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J . Am. Chem. SOC.

1991, 113, 1659-1669 1659

description is likely appropriate for all our systems. reported here and the supporting low-temperature fluorescence
At present, we are not aware of any other reasonable mecha- emission studies13 indicate, in fact, that ET in covalently linked
nistic alternatives to the proposed superexchange meckanism that porphyrin-quinone systems can take place efficiently at low
can account for the observed decay behavior of H2* Zn-Q and temperature (and in nonpolar solvents), as it does in the reaction
H2*-Zn-Q. Superexchange involving the bridge linking the donor center.28 Apparently, one of the factors that is needed is a rigid,
and acceptor has been proposed for a number of temperature-independent structure: If the model system is floppy,
The observed time constant of 55-1 IO ps is significantly faster then at room temperature E T may occur efficiently only in ge-
than expected for a 12-1 4-A edge-to-edge distance if ET proceeds ometries where the donor and acceptor subunits closely approach.
through the solvent, as discussed on the basis of the fluorescence These favorable geometries may not be accessible in a frozen
data.I3 Additionally, in our monometalated dimers, the 55-1 IO-ps solvent and the ET efficiency would be expected to decrease. T o
time constant is much faster than that observed for ET over about the extent that E T occurs predominantly through the bonds in
the same distance (and with about the same driving force) from the bridge separating the donor and acceptor, one would expect
an excited porphyrin to a benzoquinone linked by a bisbicyclooctyl to observe efficient low-temperature photoinduced E T in a wide
spacer.6i This suggests that the mediating Zn-porphyrin subunit variety of model systems. Our results on structurally rigid and
provides an excellent superexchange bridge, perhaps due to the well-defined quinone-substituted porphyrin complexes are con-
conjugated T-electron system or to the energies of the relevant sistent with this point of view.
orbitals. In any case, we have presented here a key, and we believe
clear, example, which demonstrates that a porphyrin can serve Acknowledgment. This work was supported by a grant from
very effectively as a superexchange mediator in well-defined the Robert A. Welch Foundation (F-1018 to J.L.S., the Dreyfus
complexes containing close electronic and structural relatives of Foundation (New Faculty Grant 1984 and Teacher-Scholar
the cofactors in the bacterial reaction center. Award 1988-1992 to J.L.S.; Teacher-Scholar Award 1987-1991
Aside from the specific question of superexchange, the obser- to R.A.F.), the National Science Foundation (PYI Award 1986
vation of highly efficient low-temperature charge separation is to J.L.S.),and National Institutes of Health Grants (GM 34685
of interest in its own right. There are only a few other examples to D.H. and G M 41657 to J.L.S.). R.A.F. also acknowledges
of porphyrin-based photosynthetic model systems in which this receipt of a Research Career Development Award from the NIH,
has been observed.8 Indeed, there has been considerable discussion institute of General Medical Sciences.
as to whether low-temperature charge separation can be effected
in model systems without the benefit of unusual structure or (28) Temperature-insensitive electron transfer in the bacterial reaction
energetics (i.e., driving force).8C Both the time-resolved results center is discussed in refs 2a,b,e,4~,25,26b,and 27.

Preparation and Reactions of Mn2(CO),( $-aldehyde)


Complexes
R. Morris Bullock* and Brian J . Rappoli
Contribution from the Department of Chemistry, Brookhaven National Laboratory,
Upton, New York I 1973. Received July 24, I990

Abstract: The reaction of HMn(CO)S with RMn(CO)5 (R = CH3, p-CH3C6H4,or CH2CH2CH=C(Ph)CH,) gives Mn2-
(CO),(sI-RCHO) complexes. It is suggested that these Mn2(CO),(sl-aldehyde) complexes may provide a model for a previously
unobserved intermediate in the formation of aldehydes from the hydroformylation of olefins. The 7'-aldehyde ligand is weakly
bound to the manganese, as evidenced by its facile displacement by ligands such as CO, PPh3, and CH3CN. The kinetics
of the reaction of HMn(CO)Swith (CO)SMn(CH2CH2CH=C(Ph)CH3) were studied by 'H NMR at 25 OC in C6D6. The
reaction is first-order in the manganese alkyl complex, and the rate of the reaction decreases slightly with increasing concentration
of HMn(CO)S. A negligible isotope effect ( k , / k , = 1.04 f 0.09) was found for the reaction of (CO)SMn(CH2CH2CH=
C(Ph)CH3) with DMn(CO)S. The reaction of Mn2(CO),(q1-CH,CHO) w i t h excess HMn(CO)Stakes several days at room
temperature and produces ethanol and the manganese cluster complex Mn,(CO),(p,-OEt)2(fi2-OEt).

Aldehyde and ketone complexes of transition metals have been converted them into optically active alcohols.2 Hersh and co-
known for many years, but detailed studies of the formation and workers have structurally characterized a cationic W s'-aldehyde
reactions of such complexes have only recently been reported.' complex and have demonstrated that it is an excellent catalyst
Both aldchydes and ketones can bond to metal centers by either for the Diels-Alder reaction between dienes and a@-unsaturated
?I- or q2-bonding modes (Figure I ) , and several examples of both en one^.^ I n other cases, aldehyde complexes are not directly
of thcse have bccn crystallographically characterized. observed but have been postulated as key intermediates in met-
I n a few cases, isolable aldehyde and ketone complexes have al-mediated organic syntheses. For example, Faller and co-workers
been utilized in organic synthesis. Gladysz and co-workers have
prepared optically active s2-aldehydecomplexes of Re and have
(2),(a) Fernindez, J. M.; Emerson, K.; Larsen, R. H.; Gladysz, J. A . J .
Am. Chem. SOC.1986, 108.8268-8270. (b) Garner, C. M.; Quirbs Mendez,
( I ) (a) For a review of aldehyde and ketone complexes of transition metals, N . : Kowalczyk. J. J.; Fernindez. J. M.: Emerson, K.: Larsen. R . D.; Gladysz,
see: Huang. Y.-H.; Gladysz, J . A . J . Chem. Educ. 1988, 65, 298-303. (b) J . A . J . Am. C'hem. SOC.1990. 112. 5146-5160.
For a review treating both transition-metal and main-group Lewis acid com- ( 3 ) Bonnesen. P. V.: Puckett, C. L.; Honeychuck. R . V . ; Hersh, W . H . J .
plexes of aldehydes, ketones. etc., see: Shambayati, S.; Crowe, W . E.; Am. C'hem. SOC.1989, 111,6070-6081. (b) Honeychuck, R. V . ; Bonnesen,
Schrciber, S. L. Angew. Chem., In/. Ed. Engl. 1990, 29, 256-272. P. V . ; Farahi, J.; Hersh, W . H. J . Org. Chem. 1987, 52, 5293-5296.

0002-7863/91/ 15 13- 1659$02.50/0 0 1991 American Chemical Society


I660 J . Am. Chem. Soc., Vol. I 13, No. 5. I991 Bullock and Rappoli

Scheme I

Figure 1. Resonance forms of TI- and $-aldehyde complexes.

suggested that a Mo 7’-aldehyde complex was a crucial inter-


mediate in their synthesis of optically active homoallylic alcohols!
Burkhardt, Bergman, and Heathcock proposed a Ni 7’-aldehyde
intermediate in the reaction of a Ni enolate complex with benz-
aldehyde., Pedersen and co-workers proposed an 7’-aldehyde E(20,reflux
intermediate in the V ( 11)-mediated cross-coupling of aldehydes
to produce 1,2-diok6
One of the most thoroughly investigated methods for synthesis
of aldehydes is the metal-catalyzed hydroformylation of olefins.’ hydrogenation proceeds by sequential hydrogen atom transfers
In view of the recent interest in aldehyde complexes as well as from the metal hydride to the organic substrate; metal hydrides
the long-standing interest in mechanistic details of the hydro- that hydrogenate a-cyclopropylstyrene as shown in eq 1 include
formylation reaction, the possible intermediacy of complexes
containing aldehydes directly bonded to transition metals during
the hydroformylation reaction is of substantial mechanistic im-
portance.
2 MH + H>C=C$ -
In several studies of the aldehyde-forming step of the hydro-
formylation reaction, free aldehydes have been shown to result
from a dinuclear elimination reaction between a metal hydride
and a metal alkyl complex.8 We recently discovered that
Mn,(CO),(q’-aldehyde) complexes can be prepared from reaction
of ( C 0 ) 5 M n R ( R = alkyl or aryl) and HMn(CO),., These HM(CO)$p ( M = Cr, Mo, or W), HFe(CO),Cp, HMn-
complexes differ significantly from the aldehyde complexes (CO),(PPh,), etc. While rigorously purified HMn(CO)5 behaved
mentioned above. In nearly all examples of isolable organometallic similarly to the other metal hydrides, we were surprised to find
aldehyde complexes reported to date, q2-bonding is found for that samples of HMn(CO),, which were not thoroughly dried with
neutral complexes. In contrast, cationic aldehyde complexes P,O,, resulted in the unexpected ring-opening hydroformylation
typically exhibit $-bonding. The Mn2(CO),(7’-aldehyde) com- reaction shown in eq 2. A spectroscopically observable inter-
plexes reported herein provide rare examples of isolable, neutral,
s’-aldehyde complexes. Furthermore, nearly all previously re-
ported aldehyde complexes were prepared by adding a free al-
H2C=Cb
- ’ Ph
+ 2 HMn(CO),

dehyde to a metal complex containing a weakly bound ligand. In


our synthetic method, the aldehyde is formed during the reaction,
with the R group and carbonyl being supplied from (CO),MnR
and the aldehyde H coming from the hydride of HMn(CO),. In OC-Mn-
this paper, we report the synthesis, characterization, and reactions
of these Mn2(CO)g(v1-aldehyde)complexes.
Results mediate in this reaction was identified as the manganese alkyl
Synthesis of Mn,(CO),(tll-aldehyde)Complexes. We discovered complex (CO),Mn(CH,CH2CH=C(Ph)CH3) (hereafter this
the first Mn2(C0),(7I-aldehyde) complex while carrying out a alkyl group will be abbreviated as R’ = CH2CH2CH=C(Ph)-
kinetic and mechanistic study of the hydrogenation of a-cyclo- CH,). This manganese alkyl complex, which had formed from
propylstyrcnc by a series of transition-metal hydrides.I0 This the reaction of a-cyclopropylstyrene with 1 equiv of HMn(CO)5
(eq 3), was reacting with 1 equiv of HMn(CO), (eq 4) to produce
(4) Faller, J . W.; John, J. A,; Mazzieri, M. R . Tetrahedron Lett. 1989, 30,
1769-1772.
( 5 ) Burkhardt, E. R.; Bergman. R. C.;Heathcock, C . H. Organomefallics
1990, 9, 30-44.
(6) Freudenberger, J . H.:Konradi, A. W.; Pedersen, S. F. J . A m . Chem.
SOC. 1989, 111. 8014-8016.
( 7 ) For reviews of hydroformylation, see: (a) Pruett, R . L. Acc. Chem.
Res. 1979. 17, 1-60. (b) Cornils, B. In New Syntheses with Carbon Mon-
oxide; Falbe, J., Ed.; Springer-Verlag: New York, 1980. (c) Pruett, R . L.
J . Chem. Educ. 1986, 63, 196-198.
(8) (a) Halpern, J. Acc. Chem. Res. 1982, I S , 332-338. (b) Nappa, M. Mn2(CO),(v’-R’CHO). The formation of (CO),MnR’ from
J.; Santi. R.; Halpern, J. Organomefallics 1985, 4, 34-41. (c) Warner, K . n-cyclopropylstyrene and HMn(CO), is a perplexing reaction,
E.; Norton, J. R. Organometallics 1985, 4 , 2150-2160. (d) Martin, B. D.; which has an induction period; an impurity (not yet conclusively
Warner, K . E.; Norton, J. R. J . A m . Chem. SOC.1986,108, 33-39. (e) Jones,
W. D.; Bergman, R. G.J . A m . Chem. SOC.1979,101, 5447-5449. (0 Jones, idcntified) present in the HMn(CO), appears to be necessary for
W. D.:Huggins, .J. M.; Bergman. R. G. J . A m . Chem. SOC.1981, 103, this reaction. The fact that (CO),MnR’ was being concurrently
441 5-4423.
(9) For a preliminary account of part of this work, see: Bullock, R. M . ;
Rappoli, B. J.; Samsel, E. G.;Rheingold, A. L. J . Chem. Soc., Chem. Com- ( I O ) Bullock, R. M.; Samsel, E. G. J . Am. Chem. SOC.1987, 109, 6542-
mun. 1989, 261-263. 6544; J . Am. Chem. Soc. 1990, 112, 6886-6898.
Mn2(CO)p(q’- aldehyde) Complexes J . Am. Chem. Soc., Vol. 113, NO. 5, 1991 1661

formed (eq 3) and consumed (eq 4) complicated the study of the complexes are available for comparison, but the slight elongation
latter. Details of the reaction shown in eq 3 will be published of the C=O bond of aldehydes upon VI-coordination is also ob-
separately. served in cationic ql-ketone complexes.’ In contrast, C=O bond
We recognized, however, that the formation of Mn2(C0)9- lengths of q2-aldehyde complexes are generally > 1.3 A.’ This
(VI1’-aldehyde)complexes was probably not limited to the specific suggests that the resonance form in the upper left of Figure 1 (with
example that we discovered and furthermore that such reactions a C=O double bond) is the predominant contributor for ql-
could be studied separately by reaction of appropriate (CO),MnR aldehyde complexes, while the metallaoxirane structure at the
(R = alkyl or aryl) complexes with HMn(CO),. The independent lower right of Figure 1 (with a C-0 single bond) is the pre-
synthesis of (CO),MnR’ was accomplished by the straightforward dominant resonance contributor for q2-aldehyde complexes.
route shown in Scheme I and produces the alkyl complex as a The pattern and intensities of the IR bands of the carbonyl
reasonably air-stable solid that could be purified by crystallization ligands bonded to Mn indicate an equatorially substituted
and/or sublimation. Mn2(C0)9 moiety, and this was also confirmed by the crystal
The ‘ H N M R spectrum of this independently prepared structure9 of Mn2(C0)9(~’-R’CHO).The aldehyde C=O stretch
(CO)=,MnR’complex was identical with that observed as an in- is observed as a weak band at 1640 cm-’ for Mn2(CO),(~’-
termediate in reaction 3. However, the appearance of the ‘ H CH,C,H,CHO). This band is only 72 cm-’ lower than the c=o
N M R peaks was clearly not a simple first-order pattern. For band in free p-tolualdehyde (1712 cm-I), which is also in
example, the MnCH, resonance was not a triplet as might have agreement with only a slight weakening of the C=O bond. In
been expected from coupling of equivalent protons of MnCH, to contrast, IR bands of aldehyde C=O stretches for q2-aldehyde
the vicinal allylic C H 2 protons. The chemical shifts and coupling complexes are typically found at much lower energy (- 1200 cm-I
constants were determined by computer simulation of the ‘ H or lower).’ The aldehyde IH N M R resonance is observed at 6
N M R spectrum of (CO),MnR’. Figure 2 shows the calculated 7.91 (in C6D6)for M n , ( C 0 ) 9 ( q ’ - C H , C 6 H , ~ ~(compared
~) to
and experimental spectra for the MnCH,CH,, MnCH2CH,, vinyl, 6 9.68 for free tolualdehyde in C&). These spectroscopic criteria
and methyl resonances. A Newman projection of the most stable all confirm that the ql-bonding of the aldehyde found in the crystal
conformation of (CO),MnR’ is shown in Figure 3. The dia- structure is maintained in solution.
stereotopic protons H A and H B of MnCH2 are strongly coupled The orange color of the Mn,(CO),(q’-aldehyde) complexes is
to each other ( J = 15.4 Hz), as are the geminal allylic protons due to a visible absorption band [ e g , A,, = 470 nm for Mn2-
Hc and H D ( J = 11.5 Hz). The inequivalence of these protons (C0)9(q’-CH,C6H,CHO)]. The electronic absorption spectra
does not require restricted rotation about the Mn-C or C-C of Mn,(CO)lo and substituted derivatives such as Mn2(C0)9-
bonds.” The experimental spectrum shown in Figure 2 was (PPh,) have been assigned by Levenson and Gray.I2
recorded at 23 OC, but no change in the spectrum was observed Aldehyde Displacement Reactions of Mn,(CO),( VI-aldehyde)
at -70 OC. A complete listing of coupling constants and chemical Complexes. The weak bond between the aldehyde and the
shifts is given in the Experimental Section. manganese is readily broken by reaction with donor ligands.
The successful synthesis of Mn,(CO),(q’-R’CHO) by reaction Exposure of an orange solution of Mn,(C0)9(q1-CH,C6H,CHO)
of a manganese alkyl complex with HMn(CO), suggested that to C O ( 1 atm) causes release of free tolualdehyde and fading of
similar aldehyde complexes should be available from other the solution to the yellow color of Mn,(CO),, within 30 s. Similar
manganese alkyl or aryl precursors. The reaction of (CO)=,Mn- reactions are observed with CH3CN and PPh,, giving previously
@-CH3C6H4)with HMn(CO), in hexane gave Mn2(C0),(q’- reported compounds Mn,(C0)9(CH,CN)’3 and Mn2(C0)9-
CH3C6H4CHO)(eq 5 ) in 80% isolated yield. Toluene (about 2% (PPh,).’, A qualitative indication of the mild conditions under
yield) was a minor component of this reaction. A similar reaction which the aldehyde can be displaced comes from an experiment
between CH,Mn(CO), and HMn(CO), produced Mn,(CO),- in which the reaction of Mn,(CO),(q’-R’CHO) (-0.04 M) with
(1’ - C H3CHO). C H J N (-0.3 M) was complete within a few minutes at -30

(co)~M~-+H~ + HMKO)~ - “ C in toluene-d8. The acetaldehyde complex Mn2(C0),(01-


CH,CHO) was further characterized by its reaction with C O to
give CH,CHO and Mn2(CO)loand by its reaction with tolu-
aldehyde to give Mn2(C0)9(q’-CH3C6H,cHo)and free CH,C-
HO. Preliminary experiments indicate that the aldehyde ligand
0 0 0
in these complexes is readily displaced by an excess of acetone,
dimethylformamide, dimethyl sulfoxide, triphenylphosphine oxide,
OC-Mn- Mn-co (5)
and other donors. Quantitative experiments to assess the kinetics
and thermodynamics of aldehyde displacement will be reported
later.
Physical Properties and Spectral Data of Mn2(CO),(~l- Kinetics of the Reaction of (CO),MnR’ with HMn(CO)5. The
aldehyde) Complexes. Both Mn2(CO),(~’-R’CHO)and Mn2- kinetics of reaction 4 were studied by ‘ H N M R in C6D6 at 25
(C0)9(~’-CH3C6H4CHO) can be crystallized from hexane to give “C. The rate of disappearance of (C0)5MnR’ (0.05-0.07 M) was
air-sensitive orange crystals, which are stable for > I year when determined as a function of excess HMn(CO), concentration. The
stored at -20 OC under argon. The acetaldehyde complex observed pseudo-first-order rate constants are listed in Table I .
M ~ , ( C O ) , ( V ~ - C H , C H Owas
) obtained as an orange powder; The reaction of (CO),MnR’ with a mixture of HMn(CO), and
qualitative observations indicate that the thermal stability of this DMn(CO), at 22 OC had a negligible isotope effect of k H / k D=
complex in solution is somewhat lower than those for the other 1.04 f 0.09. A pseudo-first-order plot for disappearance of
two $-aldehyde complexes. The acetaldehyde complex also de- (CO),MnR’ over the first 3 half-lives of the reaction is shown in
composes when left under high vacuum for several hours, pre- Figure 4. The rate of disappearance of (CO),MnR’ is cleanly
sumably due to the lability of the acetaldehyde ligand. The X-ray first-order, but the relative amounts of free and complexed al-
crystal structure9 of Mn,(CO),(q’-R’CHO) verified the 7 ’ - dehyde change as the reaction proceeds. More of the free aldehyde
bonding, which had been assigned on the basis of spectroscopic is observed at early reaction times, whereas the product ratio levels
data. The C=O bond length of the aldehyde is 1.216 (9) A. This out at longer times. Figure 5 shows a plot of [Mn2(CO)9(q1-
is only slightly longer than a typical C=O bond distance ( - 1.20 R’CHO)]/[total aldehyde] as a function of time.
A) for a free aldehyde. Little structural data on other ql-aldehyde The reaction between (CO),MnR’ and HMn(CO), is much
faster in CD3CTi than in C,D,. A fro7en solution of (CO),MnR’
( I I ) (a) Becker, E. D.High Resolulion N M R ; Academic Press: New
York, 1969; pp 224-228. (b) Waugh. J. S.; Cotton. F. A. J. Phys. Chem. (12) Levenson. R . A.; Gray. H . B. J. Am. Chem. Soc. 1975, 97,
1961. 65, 562-563. (c) Sanders, J. K.; Hunter, B. K. Modern N M R Spec- 6042-6047.
froscopy; Oxford University Press: Oxford, 1987; pp 299-302. (13) Koelle. U. J . Organomef. Chem. 1978. I55. 53-62.
1662 J . Am. Chem. SOC.,Vol. 113, No. 5, 1991 Bullock and Rappoli

I ' I ' I ' I ' I ' I


1.16 1.14 1.12 1.10 1.08 1.06
PPM

1 I I
2.07 2.06 2.08
PPM

1 ' 1 ' 1 ' 1 ' 1 ~ 1 - 1 . 1 3 1 - 1 . 1 3 I


2.62 2.60 2.58 2.56 2.54 2.52 5.94 5.92 5.90 5.88 5.86
PPM PPM
Figure 2. Calculated (upper) and experimental (lower) ' H NMR spectra of (CO)5MnCH,CH2CH=C(Ph)CH,: (a) MnCH2, (b) CH,, (c) MnCH2CH2,
and (d) C=CH.
Mn,(C0)9(7’- aldehyde) Complexes J . Am. Chem. Soc., Vol. 113, No. 5, 1991 1663

CH=C(Ph)CH3
20 100 180 260
Figure 3. Newman projection of (C0)5MnCH2CH2CH=C(Ph)CH3. time (minutes)
aldehyde] as a function of
Figure 5. [Mn2(C0),(q1-R’CHO)]/[total
time.

to room temperature, the color of the solution immediatetely


changed from orange to a darker orange. In addition to resonances
in the ‘H N M R spectrum for the free aldehyde, a broad (-80-HZ
line width at half-height) resonance was observed at 6 -22.1. This
resonance is assigned to HMn,(CO),,. The chemical shift of
HMn3(CO),, is similar to the bridging hydride resonance of
H,Mn,(CO)12,14which we have found to be at 6 -23.9 in C6D6.
The formation of HMn,(CO),, was also observed in experiments
involving the other two aldehyde complexes.
A
-2.5 M The concentrations of H M ~ I ( C O ) free
~ , aldehyde, and com-
plexed aldehyde determined in the kinetics experiments also
0 50 100 150 200 250 300
provide a measure of the equilibrium constant for eq 6 over the
time (minutes) course of the reaction. The equilibrium constant determined at
Figure 4. First-order plot of the rate of disappearance of (C0)5MnR’ 22 “ C for eq 6 was Kes = (1.2 f 0.1 ) X In a related
(0.06 M) in its reaction with HMn(CO)5 (0.95 M) in C6D6 at 25 O C . experiment, Keq for eq 6 was determined from the reaction of
(CO)5MnR’ and HMn(CO)5 at 8 OC in C6D6. The equilibrium
Table I. Observed Pseudo-First-Order Rate Constants for constant determined in this experiment from data points taken
Disappearance of (CO)5MnR’ in Reaction with Excess HMn(CO)s during the first half-life of the reaction did not differ appreciably
at 25 OC in C,D6 from the equilibrium constant determined at the end of the re-
[HMn(COhI, M 1 04kOb,a s - ~ action. This indicates that, under our experimental conditions,
0.54 1.9
the equilibrium in eq 6 is rapidly established, compared to the
0.95 1.3 rate of the reaction of (CO)5MnR’ with HMn(CO)5. The
2.0 1.1 equilibrium constant determined at 8 “ C was K , = ( I . 1 f 0.2)
2.6 1 .O X The small value of the equilibrium constant indicates that
Estimated error f 10% on all rate constants. HMn(CO)S is even more weakly bound to Mn2(C0)9than is the
7’-aldehyde ligand (AGO = 2.5 kcal/mol for eq 6).
(0.06 M) and excess HMn(CO), (1.7 M) in CD3CN turned yellow Reduction of Mn2(CO)9(s1-aldehyde)Complexes to Alcohols
immediately upon thawing to room temperature. A IH N M R and Related Products. In our studies of the kinetics of reaction
spectrum taken within 4 min of thawing showed complete reaction, 4, the combined yield of free and complexed aldehyde was >95%
and only resonances due to the free aldehyde were observed. The and the solutions were dark wine red when the consumption of
yellow organometallic product was identified as Mn2(C0)9(C- the alkyl complex was complete after several hours. However,
D$N) by comparison of its IR spectrum to that of an authentic when these solutions (which still contaion an excess of HMn(CO)5)
sample.13 The free aldehyde was also produced in a slow reaction are left at room temperature in the dark for 3-5 days, the wine
between the acyl complex (CO),Mn(COR’) (0.17 M) and red color of the solution fades to a somewhat lighter orange color.
HMn(CO)5 (2.6 M) in C6D6 (89% yield after 6 days at room During this time, the resonances for both the free aldehyde and
temperature). Mn2(C0)9(qt-R’CHO)decrease in intensity and are replaced by
HMn(CO)5 vs gl-Aldehyde as a Ligand on Mn2(C0)9. It was new peaks due to the formation of the alcohol R’CH20H (6040%
mentioned above that relatively weak nucleophiles such as CH,CN yield) (eq 7). Confirmation of the identity of this alcohol was
can displace the 7)-aldehyde ligand. The change in the free
aldehyde to complcxcd aldehyde ratio observed (Figure 5) in the
study of the kinetics of formation of Mn2(C0)9(71-R’CHO)
P==LJih
(CO)5Mn-Mn(CO)r
suggested an equilibrium in which HMn(CO)5 displaced the
aldehyde ligand. Direct observation of the equilibrium shown in
eq 6 was accomplished by adding an excess of HMn(CO)5 to a

+
HO

obtained by comparison of its IH N M R spectrum with that of


an authentic sample prepared as shown in eq 8.

ChDhsolution of Mn,(CO),(ql-R’CHO). When a frozen solution (14) Johnson, B. F. G.; Johnston, R . D.; Lewis, J.; Robinson, B. H.; Ola-
containing HMn(CO)5 and the aldehyde complex was warmed zagasti. M.; Muetterties, E. Inorg. Synrh. 1970. /2, 43-45.
1664 J. Am. Chem. Soc., Vol. 113, No. 5, 1991 Bullock and Rappoli

HO ui-
h (1) LIAIH,
(2) H,O HO d L t , (8)
( 1 .O M) was carried out for 5.5 days at room temperature, and
the solution was then treated with CH,CN. The volatile products
CD,CHO and CD,CH,OH were identified by 'HN M R and by
GC/MS. In both of these deuterium-labeling experiments, the
An analogous reduction of acetaldehyde to ethanol was also
' H N M R spectra verified the expected deuterium incorporation
observed with Mn2(C0),(q1-CH3CHO). A C6D6 solution of
into the ethoxy groups of Mn3(CO)g(p3-OEt)2(p2-OEt), as shown
(CH,)Mn(CO)5 (0.35 M) and HMn(CO), (1.8 M) had turned in eq 10 and 1 1 .
dark wine red after 21 h at room temperature, giving Mn2-
(CO),(vI-CH,CHO) (72%) and free C H 3 C H 0 (21%). The free
and complexed aldehydes were nearly completely consumed after
7 days. Along with other peaks to be discussed later, two very
broad, overlapping resonances were observed at 6 3.62 and b 3.33.
Addition of CH3CN resulted in the coalescence of these resonances
to a broadi5 singlet at 6 3.42. This resonance is assigned as the
C H 2 group of ethanol: the yield of ethanol was 41% based on IH
N M R integration vs an internal standard. Further spectroscopic
data supporting this assignment are given in the Experimental
Section. We suggest that an ethanol complex (Mn,(CO),(EtOH))
is formed initially and that the addition of CH3CN displaces the
weakly coordinated alcohol ligand to give free EtOH. Further
evidence in support of Mn2(C0),(EtOH) is presented below.
Along with the braod peaks discussed above and assigned to
free and coordinated ethanol, two well-resolved quartets and
accompanying triplets were also observed in the reaction of 1 DMn(C0)s
Mn2(CO),(v1-CH,CHO) with HMn(CO)5. These resonances are
due to Mn,(CO),(p3-OEt),(p2-OEt). This assignment was con-
firmed by comparison of the IR and IH N M R spectra of Mn,-
(CO),(p,-OEt),(p,-OEt) from reaction 9 with those of an au- CH3CDzOD +
+
M~~(CO)~(~~,-OCDZCH,)Z(~~~~D~CH,)
(1 1)

thentic sample.I6 The 44% yield of this Mn, cluster, together


with the 41% yield of EtOH mentioned above, accounts for an The data presented above provide evidence for an ethanol
85% combined yield based on CH,Mn(CO),. complex Mn,(CO),(EtOH) as one of the products from the re-
action of CH,Mn(CO), with HMn(CO)5. Additional supporting
evidence for this alcohol complex comes from direct observation
of the reversible reaction shown in eq 12. When EtOH was added

$ya3
,o=c\H
(CO)+4n--Mn(C0)4 + CH,CH20H -
CH2CHj (9)
I

to a C6D6 solution of Mn2(CO),(v1-tolualdehyde), the color of


the solution turned from dark wine red to a lighter red-orange
and resonances due to free tolualdehyde and coordinated CH3C-
CH,CH, H 2 0 H were observed. The O H resonance of coordinated EtOH,
which appeared as a triplet at 6 4.41, was absent in an analogous
Deuterium-labeling experiments provided further confirmation experiment carried out with C H 3 C H 2 0 D . When the volatile
of the formation of ethanol in the reaction of CH,Mn(CO), with components were evaporated on a vacuum line and C6D6 was
HMn(CO)S. The reaction of CH3Mn(CO)5 (0.20 M) with readded, all of the peaks assigned to Mn,(CO),(EtOH) disap-
DMn(CO), ( 1 .o M) in C6D6 gave Mn2(C0)9(qi-CH,CDO)(61%) peared but the resonances for Mn,(CO)g(ql-tolualdehyde) re-
and free CH,CDO (19%) along with unreacted CH,Mn(CO), mained. This verifies that the reaction is reversible, since EtOH
(8%) after 24 h at room temperature. After 5.5 days, C H J N (bp 78 'C) is readily evaporated on the vacuum line along with
was added to displace coordinated aldehyde and alcohol. The the C6D6 solvent, whereas less volatile tolualdehyde (bp 204 " c )
organic products CH,CDO and CH3CD20D/CH3CD20Hwere was not pumped off, but recoordinated to the manganese. A Kq
verified by ' H N M R and by G C / M S . A complementary ex- = 0.4 was determined for eq 12, indicating that the alcohol is even
periment was carried out with D labels in the methyl group: The more weakly bound to the Mn2(C0), moiety than is the aldehyde.
reaction of CD,Mn(CO), (0.16 M, >99% D) and HMn(CO), A stronger binding constant of aldehydes compared to alcohols
was also found in cationic Re complexes studied by Gladysz and
(I5 ) It is not clear why the resonances for free ethanol are broadened, but co-workers." They recently reported that the benzyl alcohol ligand
rapid exchange of free and coordinated ethanol is ruled out,bl the fact that of (Cp)Re(NO)(PPh3)(PhCH20H)+BF4-is displaced by benz-
the coordinated ethanol resonances are well-resolved. We note that the res- aldehyde to produce (Cp)Re(NO)(PPh3)(q2-PhCHO)+BF4-.
onances due to free aldehyde are also broadened compared to complexed Organometallic complexes with alcohol ligands are relatively rare,
aldehyde in these experiments. We considered the possibility that the alcohol
and aldehyde were in rapid equilibrium with the hemiacetal, but this does not but there are a few examples of well-characterized cationic or-
appear to be responsible for the broadening, since a C,D, solution of p- ganometallic complexes with alcohol ligands.'*
tolulaldehyde and ethanol exhibited sharp resonances (in the absence of any
Mn complexes), even in the presence of a trace of acid.
(16) (a) Abel, E. W.; Farrow, G.; Towle, I . D.H. J . Chem. SOC.,Dalton (18) Siinkel, K.; Urban, G.; Beck, W. J . Organomei. Chem. 1985. 290,
Trans. 1979,71-73. (b) Abel, E. W.; Towle, 1. D.H.; Cameron, T. S.;Cordes, 231-240. (b) Crabtree, R . H.; Demou. P. C.; Eden, D.;Mihelcic, J . M.;
R. E. J . Chem. Soc.. Daliort T r a m . 1979, 1943-1949. Parnell, C. A,; Quirk, J. M.; Morris, G. E. J . Am. Chem. SOC.1982, 104,
(17) Agbossou, S.K.; Smith, W. W.; Gladysz, J . A. Chem. Ber. 1990, 123, 6994-7001. (c) Grundy, K. R.; Robertson, K. N . Inorg. Chem. 1985, 24,
1293-1 299. 3898-3903.
Mn2(CO)9(v‘ -aldehyde) Complexes J . Am. Chem. SOC.,Vvi. ‘113, No. 5, 1991 1665
Scheme I1 Scheme 111

k4 1I k.4
n
U

produce a coordinatively unsaturated manganese acyl intermediate,


In a control experiment, no hydrogenation of free acetaldehyde which then reacts with HMn(CO), to produce the aldehyde
to ethanol was observed when a solution of C H 3 C H 0 and a large complex (Schemes I1 and 111; the empty square is used to represent
excess of HMn(CO), was kept at room temperature for 6 weeks. a vacant coordination site). Applying the steady-state approxi-
mation to the intermediate acyl complex gives the rate law shown
Discussion in eq 13. This rate law can give overall first-order, second-order,
Formation of $-Aldehyde Complexes in Dinuclear Elimination
Reactions. The isolation of these Mn2(CO)9(~’-aldehyde)com-
plexes stands in marked contrast with several closely related
reactions of metal alkyls and metal hydrides which give free
aldehydes. Bergman and co-workers reported the formation of
C H 3 C H 0 from reaction of CH,Mo(CO),(C,H,) with HMo-
(CO)3(C5H5).8e-fHalpern and co-workers found that the reaction
of (p-CH30C6H4CH2)Mn(CO)swith HMn(CO), in CH3CN or mixed kinetics depending on the relative magnitudes of the rate
produced p-CH30C6H,CH2CH0 and Mn2(CO)9(CH3CN).8a,b constants. In cases where k-, >> k2[MH], then kobs = ( k l k 2 /
In both of these cases, kinetic and mechanistic evidence indicated k-,)[MH]; the reaction rate will increase with increasing [MH],
that alkyl migration generated a coordinatively unsaturated acyl and the reaction will obey second-order kinetics. On the other
complex, which then formed the free aldehyde by reaction with hand, when k2[MH] >> k q , then kobs= k , , so the overall reaction
the metal hydride. In the latter study, however, reactions of other is determined by the rate of alkyl migration and will be inde-
closely related benzylmanganese complexes with manganese hy- pendent of [MH]. We suggest that the kinetic data summarized
drides gave alkanes instead of aldehydes and several different in Table I indicate that k2[MH] >> k-, in our reactions. However,
mechanistic pathways were identified. Halpern called attention the data in Table I show that the rate increased slightly with
to the diversity of these reactions and noted that “relatively modest decreasing [ H M ~ I ( C O ) ~ This
] . unusual result is not predicted
changes in ligands, solvent, or C O concentration may result in by the rate law and requires an additional explanation. We
essentially complete crossover from one pathway to another.”8b propose that, in each of our kinetic experiments, kob = k , but that
Our results provide additional support for this statement, since the value of k , decreases slightly at higher [HMn(CO),] due to
we observe Mn2(CO)9(~1-aldehyde) complexes only when the a solvent effect. The high concentrations of [HMn(CO),] used
reactions are carried out in nondonor solvents in the absence of in these kinetics experiments cause the nature of the medium to
CO. I f the reactions are carried out in CH,CN, or in benzene vary considerably as [HMn(CO),] is changed. For example, in
or hexane under CO, then only the free aldehyde is observed. In the kinetics experiment with [HMn(CO),] = 2.6 M, the solution
view of the considerable amount of previous work on reactions was 39% HMn(CO), by volume. At the lower end of the con-
of metal alkyls with metal hydrides (and especially the seminal centrations used for the kinetics study ([HMn(CO),] = 0.54 M),
role that studies of alkyl migration reactions of (CO),MnR the solution was oniy 9% HMn(CO), by volume. As discussed
complexes have played in the development of a detailed under- below, large solvent effects on other migration reactions are
standing of migratory insertion reactions), it is perhaps surprising commonly observed. The negligible isotope effect that we found
that these Mn2(CO)g(vl-aldehyde)complexes were discovered from reaction of (CO),MnR’ with HMn(CO),/DMn(CO), is also
from the straightforward reaction of (CO)5MnR with HMn(CO),. consistent with the interpretation that kob = k , . The step involving
Norton and co-workers have found that rate constants for M-H (D) bond cleavage ( k 2 in Scheme 11 or k 3 in Scheme I l l )
reaction of EtRe(CO), with HW(C0)3Cp, HMn(CO)S, or occurs after the rate-determining step, so any isotope effect on
HRe(CO), (all of which give EtCHO) are the same and fur- this step would not affect the observed kinetics.
thermore that the rate of these reactions is equal to the rate of The rate constant of k , = (1-2) X s-’, which we found
migration of the ethyl group to form a Re acyl complex.8d A study in the reactions of (CO),MnR’, is significantly larger than the
of the kinetics of the reactions of several metal hydrides with the rate constant for methyl migration of CH3Mn(CO),, which was
spectroscopically observable metal acyl complex Et(C=O)Re- reported to be k = 2.18 X s-’ at 25.5 O C in mesitylene.*O
(CO),(CH3CN) indicated that the metal hydrides reacted as These relative rates conform to the general trend that ethyl and
nucleophilcs toward the solvated acyl intermediate. A quantitative
scalc of rclativc nucleophilicity of sevcral metal hydrides was (19) For reviews of CO insertion reactions, see: (a) Calderazzo. F. Angew.
established from this work. Chrm., I n [ . Ed. Engl. 1977, 16. 299-31 I . (b) Kuhlmann. E. J.; Alexander,
Formation of a coordinativcly unsaturated metal acyl intcr- J. J . Coord. Chem. Rev. 1980. 33, 195-225. (c) Wojcicki. A. Ado. Organomef.
mediate has been established as the initial step for the formation Chem. 1973. I / . 87-145. (d) Alexander, J . J . I n The Chemistry of the
o f f r e e aldehydes in the reactions cited above. We propose that Mefal-Carbon Bund; Hartley. F. R..Patai. S., Eds; John Wiley and Sons:
N e w York, 1985; Vol. 2, pp 339-400.
thc mcchanism of formation of the Mn2(CO),(~’-aldchydc) (20) Mawby, R. J.; Basolo, F.; Pearson, R . G.J. Am. Chem. Soc. 1964,
complcxcs involvcs migrationi9 of thc alkyl (or aryl) group to 86. 3994-3999.
1666 J . Am. Chem. SOC.,Vol. 113, No. 5, 1991 Bullock and Rappoli
longer chain alkyl groups undergo alkyl migration reactions faster aldehyde at the end of the reaction compared to that at early
than methyl. For example, Calderazzo and Cotton found that reaction times.
the rate of migration for EtMn(CO), was 13 times faster than Regardless of the detailed mechanism of formation of the
that for CH,Mn(CO), (at 30 OC in 2,2'-dimethoxydiethyl ether).21 Mn2(CO)9(ql-aldehyde) complexes, our observation of facile
A common feature of alkyl migration reactions is that they displacement of the aldehyde ligand of the Mn2(CO)9(7'-aldehyde)

-
proceed much faster in donor solvents. The rate of methyl mi-
gration of CH3Mn(CO)Sis lo4 times faster in dimethylform-
amide compared to mesitylene.,O We find that the reaction of
complexes by CH3CN and other nucleophiles provides a plausible
explanation of why these aldehyde complexes are isolable, whereas
closely related experiments have led to the observation of only
(CO)SMnR' with HMn(CO)5 is markedly accelerated in aceto- free aldehydes. A crucial factor in the successful isolation of the
nitrile compared to that in benzene. Wax and Bergman have Mn2(CO)9(?'-aldehyde) complexes is the lack of donors (such as
studied the kinetics of the formation of Cp(CO)2(PMePh2)Mo- CH,CN), which bond to the coordinatively unsaturated inter-
COCH, from Cp(CO)3MoCH3 and PMePh, in T H F and in mediate Mn2(C0)9 more strongly than the aldehydes.
several methyl-substituted T H F solvents (Le., solvents of com- The trinuclear cluster complex HMn3(C0)14can be considered
parable polarity but significantly different donor abilities).22 The to be comprised of Mn2(C0)9with HMn(CO)S as a ligand. The
results of their study established that the solvent coordinates to bonding in the Mn(p-H)Mn bridge involves a 3-center, 2-electron
the metal and assists the migratory CO insertion. Further interaction. The L-shaped geometry of the three Mn atoms
clarification of the role of donor solvents in the promotion of depicted for HMn3(C0),4 is analogous to the structures of
migratory insertions was provided by Halpern and co-workers, HRe2Mn(C0)1424and HReMn2(C0),4,2swhich have been es-
who found that nucleophilic solvents not only catalyze the for- tablished by crystallography. Warner and Norton reported that
mation of coordinatively unsaturated acyl complexes but also HMnRe,(CO)], and C H 3 C H 0 resulted from the reaction of
dissociate prior to trapping by the metal hydride.23 CH3Mn(CO)Swith HRe(CO), in benzene, whereas the same
It is possible that aldehyde complexes are unobserved inter- reaction in CH3CN gave the free aldehyde and (CO)SReMn(C-
mediates in all of the reactions discussed above in which aldehydes O)4(CH3CN).8C We have found that HRe(CO)s reacts with
are formed from metal alkyls and metal hydrides but that their Mn2(C0)9(7'-CH3C6H4CHO)to produce HReMn,(CO) 14 and
high reactivity precludes their observation in the presence of free t o l ~ a l d e h y d e .The
~ ~ displacement of the 7'-aldehyde ligand
sufficiently reactive nucleophiles. Aldehyde complexes may also by HRe(CO)5 clearly indicates the thermodynamic preference
be unobserved intermediates in the formation of free aldehydes of HRe(CO), over an aldehyde, as a ligand on Mn2(C0)9. Since
in catalytic hydroformylations. Note that these manganese al- the value of AGO = 2.5 kcal/mol for eq 6 indicates that the
dehyde complexes react rapidly with l atm of CO. Considering aldehyde bonds more strongly to Mn2(C0)9than does HMn(C0)5,
the generally higher reactivity observed for (CO),CoR complexes the order of binding preference to the unsaturated Mn2(C0)9
compared to those for related ( C 0 ) 5 M n R compounds, it seems moiety is established as HRe(CO)S > 7'-CH3C6H4CH0 >
unlikely that analogous C ~ ~ ( C O ) , ( ~ ~ - a l d e h ycomplexes
de) could H M n (CO) 5 .
be directly observable under the high pressures of C O typically We have recently reported the preparation of X-ray crystal
utilized in catalytic hydroformylations. structure of an unusual Re,(CO)9(7'-aldehyde) complex, which
Although our results suggest that an aldehyde complex is the was prepared by hydroformylation of the CEC bond of
initially formed product, we cannot rigorously distinguish between (C,HS)(PMe3)2Ru(C=CCH3)by HRe(C0)s26(eq 15). In spite
the closely related mechanisms shown in Schemes I 1 and 111. In
Scheme 11, Mn2(CO),(7I-R'CHO) is formed directly in the step
with rate constant k 2 . The initially formed products in Scheme Q I
+ 2 HReCOI,
111 are the free aldehyde and the coordinatively unsaturated Ru ___L

M e P j \c+c
intermediate Mn2(C0)9 ( k 3 , Scheme 111). Both schemes have
MelP
the alkyl migration ( k , ) as the first step; similarly the steps with
,
"
C
'
rate constants k4 and k 5 , which establish the equilibrium of eq
6, are the same in the two mechanisms. In principle, the me-
chansisms of Schemes 11 and 111 could be distinguished if the
direction from which the equilibrium of eq 6 is approached could
be determined, but experiments to distinguish between these
possibilities are thwarted by the fact that the equilibrium of eq
6 is rapidly established under the experimental conditions. The
rate of reaction of Mn2(CO),(7I-R'CHO) with CH3CN is much
faster than the rate of formation of the aldehyde complex. Since
this aldehyde displacement probably proceeds by a dissociative
mechanism involving the intermediacy of coordinatively unsatu-
rated Mn2(C0),, this implies that the k4/k-4 equilibrium of
Schemes I I and 111 (as well as the overall equilibrium of eq 6) of the completely different synthetic procedures used to prepare
is rapidly established. The fact that Kq for eq 6 (measured directly them, there are some striking similarities between the Mn2 and
by NMR) remained constant over the course of the reaction also Re2 aldehyde complexes. Both complexes contain an aldehyde
verifies that the equilibrium of eq 6 was rapidly established in 7'-bonded to a group 7 metal, and both are proposed to form by
all of our experiments. The data are therefore consistent with reaction of a metal hydride with a coordinatively unsaturated metal
either direct formation of the aldehyde complex ( k 2 ,Scheme 11) acyl intermediate.
or formation of the free aldehyde, which then coordinates to Comparison of M~~,(CO)~(q'-aldehyde) Complexes with Other
Mn2(C0), ( k 4 , Scheme 111). Aldehyde Complexes. These Mn2(CO),(7'-aldehyde) complexes
The change in the free to complexed aldehyde ratio (Figure are rare examples of 7,-bonding of an aldehyde in a neutral
5) is explained by the equilibrium of eq 6. The increase in organometallic complex, since most of the previously reported
[HMn3(C0),4]as the reaction proceeds drives the equilibrium neutral aldehyde complexes of transition metals exhibit 7*-
of eq 6 to the left, resulting in a larger amount of complexed bonding.' In contrast, most of the previously reported cationic
organometallic aldehyde complexes are ?'-bonded; examples in-
(21) Caldcrazzo. F.; Cotton, F. A . Abstr. Int. ConJ Coord. Chem.
Stockholm, 1962; Paper 6H7 (cited on page 101 of ref 19c). (24) Churchill, M . R.; Bau, R . Inorg. Chem. 1967, 6 , 2086-2092.
(22) Wax, M . J.; Bergman, R. G. J . Am. Chem. SOC.1981, 103, (25) Albinati, A.; Bullock, R . M.; Rappoli, B. J . ; Koetzle, T. F. Inorg.
7028-7030. Chem.. in Dress.
(23) Webb, S. L.; Giandomenico, C. M.; Halpern, J . J . Am. Chem. SOC. (26) Bhock, R. M.;Ricci, J. S.; Szalda, D. J . J . A m . Chem. Sor. 1989,
1986, 108, 345-347. 1 1 1 , 2141-2143.
Mnz(CO)9(7'-aldehyde) Complexes J . Am. Chem. SOC.,Vol. 113, No. 5. 1991 1661
clude (Cp)(CO),Mo(7'-PhCHO)+, 27 (CO),Re(v'-CH,CHO)+, 27 (C0)9(k3-OEt)2(~2-OEt). The formation of alcohol (and alkoxide)
(NO)(PMe3)(CO), W( 71-CH2=CHCHO)+, ( PPh3),(CO) Ir- products from Mn2(CO)9(v1-aldehyde)complexes is very slow,
( v ' - C H , C H = C H C H O ) + , 2 8 and several Cp(CO),Fe(v'- even in the presence of a large excess of HMn(CO)s. The primary
aldehyde)+ c ~ m p l e x e s . ~Since
. ~ ~ the choice of bonding mode is importance of the aldehyde hydrogenation in our system is due
influenced by a metal's oxidation state and ligands as well as the to its relevance to the formation of alcohols in the hydroformylation
overall charge, the trend of 7'-bonding for cationic aldehyde reaction, since it is not attractive or feasible as a method for
complexes vs ?,-bonding for neutral complexes is not an infallible synthesis of alcohols, especially in comparison to more efficient
rule but only a generalization based on the low oxidation state and widely applicable methods developed by others.
organometallic complexes studied to date. In contrast to the
tendency of neutral metal carbonyl complexes in low oxidation Summary and Conclusions
states to favor V2-bonding,aldehyde complexes of TiCI, and other The reaction of ( C 0 ) 5 M n R (R = alkyl or aryl) with HMn-
"hard" metal centers in high oxidation states normally exhibit (CO), in noncoordinating solvents produces Mn2(CO),(q1-
7'-bonding for aldehydes.' aldehyde) complexes. The aldehyde ligand is weakly bonded to
Recent studies have provided some insight into interconversions the manganese, as evidenced by facile displacement by CO, PPh,,
between q2- and 7'-bonding modes of aldehydes and ketones. CH,CN, etc. The isolation of the aldehyde complexes in these
Gladysz and co-workers recently reported the equilibration of 7,- reactions contrasts with previously reported reactions in which
and ?'-isomers of the aromatic aldehyde complexes (Cp)- a dinuclear elimination reaction between metal alkyls and metal
(NO)(PPh3)Re(RCHO)+.30Taube and co-workers found that
( N H , ) , O S ( ~ ~ - C H , C ( = O ) C H ~undergoes
)~+ an 7'- v2 isom-
hydrides resulted in free aldehydes. It is suggested that the
Mn2(C0)9(q1-aldehyde)complexes may provide a model for

-
erization upon one-electron reduction; the kinetics of the oxida-
tively induced q2 1' isomerization of (NH3)sO~(72-CH,C(=
O)CH,,+ were also r e p ~ r t e d . ~ '
previously unobserved intermediates in the formation of aldehydes
from the hydroformylation of olefins.

Hydrogenation of Aldehydes to Alcohols. The predominant Experimental Section


reaction observed with the Mn,(CO),(vl-aldehyde) complexes is General Procedures. All manipulations were carried out under an
displacement of the weakly bound aldehyde ligand by CO, PPh,, atmosphere of nitrogen or argon with use of Schlenk or vacuum-line
and nucleophilic solvents such as CH,CN. In all of these cases, techniques or in a Vacuum Atmospheres drybox. N M R spectra were
recorded on a Bruker AM-300 spectrometer (300 MHz for IH). 1R
the free aldehyde is formed. These reactions contrast with the spectra were recorded on a Mattson Polaris FT-IR spectrometer or a
hydrogenation of the aldehyde ligand observed when Mn2- Nicolet MX-I spectrometer with CaF, cells. Toluene, THF, Et,O, and
(CO),($-CH,CHO) or Mn2(C0)9(7'-R'CHO) undergoes further hexane were distilled under nitrogen from Na/benzophenone. C6D6was
reaction with HMn(CO),. Hydrogenation of aldehydes to alcohols dried over NaK, stored over (Cp,TiCI)2Zn(C1)2,3Sand vacuum-trans-
is commonly observed in catalytic hydro for my la ti on^.^ The ferred into the N M R tubes. Ph(CH,)C==CHCH2CH2Br was prepared
amount of aldehyde hydrogenation observed under catalytic as reported previously.I0 @-CH,CaH4)Mn(CO)s36awas prepared ac-
conditions is a sensitive function of temperature, pressures of CO cording to the general procedure reported by Stewart and TreichePbfor
and H,, etc. Alcohol formation is sometimes an undesired side @-XC,H,)MII(CO)~compounds. Elemental analyses were carried out
reaction, but in other cases reaction conditions have been optimized by Galbraith or Schwarzkopf Laboratories. HMn(CO)S was prepared
by a published proceduresCand purified by vacuum transfer from P 2 0 s
to maximize the yield of alcohols. As clearly as 1962, an v2- several times. This hydride was stored under vacuum a t -20 O C in the
aldehyde complex ( HCo(C0),(v2-RCHO)) was proposed as an dark and vacuum-transferred immediately prior to each use. CH,Mn-
intermediate in the hydrogenation of aldehydes to alcohols cat- (CO), and CD,Mn(CO), were prepared by M. A. Andrews for an earlier
alyzed by C O ~ ( C O ) , . ~ ~ work.)' Cr(acac), (0.07 M ) was used in I3C N M R spectra as a relax-
Bonding of an aldehyde to a transition metal (or main-group ation agent.3s I3C N M R spectra of Mn carbonyl complexes were carried
Lewis acid) activates the carbonyl group toward attack by hydride. out at low temperature ("thermal d e c o ~ p l i n g " in
) ~ order
~ to minimize
Reetz and co-workers calculated a higher positive charge density line-broadening effects from the ,,Mn ( I = 5 / 2 ) quadrupole. EtOD
on the carbonyl ctirbon of BF, adduct of acetaldehyde, compared (Aldrich) was used as received.
to free acetaldehyde.,, Gladysz and co-workers have demon- Ph(CH,)C=CHCH2CH2C02H. A solution of Ph(CH,)C=
strated that hydride donation (from the formyl complex (Cp)- CHCH2CH2Br(6.0 g, 0.027 mol) in E t 2 0 (60 mL) was added dropwise
to a flask containing Mg (0.94 g, 0.039 mol). The mixture was refluxed
Re( NO)( PPh,)CHO) to optically active aldehyde complexes for I h and then treated with an excess of gaseous C 0 2 . A saturated
(Cp)Re(NO)(PPh,)(q2-RCHO)+results in clean conversion to aqceous solution ( I O mL) of NH4CI was added, followed by addition of
optically active alkoxide complexes.2 It is possible that the alcohol dilute aqueous HCI (30 mL). The product was extracted into E t 2 0 . This
formed in our reactions of Mn2(CO)9(7'-aldehyde) complexes organic solution was then extracted with aqueous NaOH, and the basic
results from initial hydride donation from HMn(CO)S to the solution was neutralized with HCI. This aqueous solution was extracted
7'-aldehyde, giving an alkoxide complex that could be subsequently with E t 2 0 , and the E t 2 0 solution was dried (MgS04). The E t 2 0 was
cleaved by 1 equiv of HMn(CO), (acting in this case as a proton removed by evaporation, and recrystallization from hexane gave Ph-
source) to produce the alcohol. We have shown that HMn(CO), (CH3)C=CHCH2CH2C02H as a white solid. Yield: 2.78 g (0.0146
and other metal hydrides can function as efficient stoichiometric mol, 55% unoptimized). IH N M R (C6D6): 6 11.5 (br s, I H, C 0 2 H ) ,
7.3-7.1 (m, 5 H, aromatic), 5.58 (tq?' J H H = 7 Hz, 4JHH = 1.3 Hz, I H,
hydride donors to carbocations formed by protonation of certain C=CH), 2.28 (q, J = 7 Hz, 2 H, C=CHCH,), 2.13 (m, 2 H,
hindered olefins.34 However, this mechanistic probability is CH2C02H), 1.81 (m, 3 H, CH,).
speculativc, sincc we do not presently understand the details of CICOCH2CH2CH=C(Ph)CH,. SOCI, (2.6 mL, 0.069 mol) was
the formation of the alcohols or of the cluster complex Mn,- added to Ph(CH3)C=CHCH2CH2C02H(1.27 g, 6.68 X IO-, mol). No
solvent (other than SOCI,) was used, and throughout this reaction N 2
was bubbled through the reaction mixture in order to remove the HCI
(27) Appcl, M.;Sacher, W.; Beck, W . J . Orgonomer. Chem. 1987, 322,
351-356. that is formcd. (If the HCI i5 not removed, it adds to the C=C bond
(28) Yang, K . J.; Chin, C. S. Inorg. Chen. 1987, 26, 2732-2733. and the saturated acyl chloride CIC0(CH2),C(CI)(Ph)CH, results.)
(29) (a) Foxman, B. M.; Klemarczyk, P. T.; Liptrot, R. E.; Rosenblum. After the solution was stirred at room temperature for 30 min. additional
M. J . Orgunomel. Chem. 1980, 187, 253-265. (b) Schmidt. E. K. G.; Thiel,
C. H. J . Orgunomel. Chem. 1981, 209, 373-384.
(30) Quirds Mtndez. N.; Arif, A. M.; Gladysz, J. A,, submitted for pub- (35) Sekutowski, D. G.: Stucky, G. D. Inorg. Chem. 1975, 9, 2192-2199.
lication. We thank Prof. Gladysz for a preprint of this paper. (36) (a) Beck, W.; Hieber, W.; Tengler, H. Chem. Ber. 1%1, 94, 862-872.
(31) Harman, W. D.;Sekine, M.;Taube. H. J . Am. Chem. Soc. 1988, 110, (b) Stewart. R. P.: Treichel, P. M. J . Am. Chem. SOC.1970. 92, 2710-2718.
2439-2445. (37) Andrews, M . A.; Eckert, J.; Goldstone, J . A,; Passell, L.; Swanson,
(32) (a) Mark6 1.. Proc. Chem. SOC.1962, 67-68. (b) Aldridge. C. L.: B. J . Am. Chem. SOC.1983. 105. 2262-2269.
Jonassen, H. 6 . J . Am. Chem. SOC.1963, 85, 886-891. (38) (a) Gansow. 0. A.; Burke, A. R.: LaMar, G.N. J . Chem. Soc., Chem.
(33) Rcctz. M. T.; Hiillmann, M.; Massa, W.; Berger, S.; Rademacher, Cummun. 1972, 456-457. (b) Levy. G .C.; Cargioli. J. D.J. Mogn. Reson.
P.; Hcymanns, P. J . Am. Chem. SOC.1986. 108. 2405-2408. 1973, 10. 231-234.
(34) Bullock. R. M.; Rappoli, B. J. J . Chem. Soc.. Chem. Commun. 1989, (39) Todd, L. J.; Wilkinson. J . R. J . Orgonomer. Chem. 1974, 80, C31-
1447- 1448. c34.
1668 J. Am. Chem. SOC.,Vol. 1 1 3, No. 5, 1991 Bullock and Rappoli
S 0 C l 2 (2.4mL) was added. After the solution was stirred for an ad- hydroformylation reaction. Spectroscopic data are provided here for
ditional I h, the volatiles were removed by evaporation, leaving comparison with the other aldehyde complexes. 'H NMR (C6D,): 6 8.47
CICOCH2CH2CH=C(Ph)CH3 as an amber liquid (1.42g, -100% (s, 1 H, CHO), 5.13 (t, J = 7 Hz, 1 H, C=CH), 1.75 (4. partially
crude yield). Further purification can be. accomplished by distillation (95 overlapped with methyl singlet at 6 1.72,J = 7 Hz, 2 H, C=CHCH2),
"C, 0.1 mmHg) to give the product as a clear liquid. ' H NMR (CDCI,): 1.72 (s, CH,), 1.54 (t, J = 7 Hz, 2 H, CH,CHO). "C{lH] NMR
6 7.4-7.2 (m, 5 H, aromatic), 5.66 (tq, 'JHH = 7.3 Hz, ,JHH = 1.3 Hz, (toluene-d,, -40 "C): 6 226.8 (s, 2 Mn(CO)), 222.9 (s, 5 Mn(CO)),
1 H, C=CH), 3.02 (t, J = 7.3 Hz, 2 H, CICOCH2), 2.59 (q, J = 7.3 219.4(s, 1 Mn(CO)), 216.2(s, 1 Mn(CO)), 215.7 (s, CHO), 142.9 (s,
Hz, 2 H, CICOCH2CH2), 2.06 (singlet with some unresolved fine ipso), 124.0(aromatic or alkene carbon, remainder of the aromatic and
structure, 3 H, CH,). alkene carbons obscured by the solvent resonances), 44.8(s, CH2CHO),
(C0),Mn(COCH2CH2CH=C(Ph)CH3). A solution of Mn2(CO),, 25.3(s, C=CHCH2), 15.6 (s, CH,). IR (hexane): 2091 w, 2024 s, 2005
(1.29g, 3.31 X IO-' mol) in T H F ( 1 5 mL) was treated with NaK (0.4 m, 1993 s, 1982 s, 1974 m, 1974 m, 1968 m, 1945 w sh, 1939 w, 1675
g) and stirred at room temperature for 90 min to give [Mn(CO),]-. The w cm-I. UV-vis (cyclohexane): A, 340 nm (c = 1.1 X IO4 M-' cm-' 1,
solution was filtered through Celite, and the volume was reduced to about 462 (2.2X lo3). Anal. Calcd for C2,HI4Mn2Olo:C, 47.04;H, 2.63.
2 mL by evaporation of the THF. E t 2 0 (20 mL) was added, and the Found: C, 46.82;H, 2.80.
solution was cooled to -78 "C and treated with a solution of Ph(CH,)C=CHCH2CH2CH20H. E t 2 0 (20 mL) and LiAIH, (6.0
CICOCH2CH2CH=C(Ph)CH3 (1.29g, 6.18 X IO-' mol) in E t 2 0 (2 mL of a 1.0 M T H F solution, Aldrich) were added to a three-neck flask,
mL). This solution was stirred at -78 OC for 30 min, followed by which was fitted with a reflux condenser and a dropping funnel con-
warming to -1 5 "C and stirring for 1 h more to give a yellow suspension. taining Ph(CH3)C=CHCH2CH,C02H (1.07g, 5.6 X IO-' mol) in Et,O
The solvent was evaporated, and the yellow-orange solid was crystallized (20 mL). The solution of the carboxylic acid was added dropwise to the
from CH2C12/hexane to give a pale yellow solid (2.048g, 90% yield). LiAIH, over IO min, at a rate that maintained the solution at reflux.
Further purification can be carried out by flash chromatography on silica After the solution was stirred for an additional 2 h, the reaction was
gel with 1:2 CH2C12/hexane. ' H N M R (C6D6): 6 7.3-7.1 (m, 5 H, quenched with EtOAc (2 mL) followed by isopropyl alcohol (2 mL).
aromatic), 5.64 (t, J = 7 Hz, 1 H, C=CH), 2.77 (t, J = 7.1 Hz. 2 H, Water (50 mL) was added, and the reaction mixture was extracted with
MnCOCH2), 2.31 ( q , J = 7.1 Hz, 2 H, MnCOCH2CH2),1.86(s, 3 H, E t 2 0 (3 X 30 mL). The organic layer was separated, dried (MgSO,),
CH,). "Cl'H] NMR (CD2C12,-43 "C): 6 247.4 (s, acyl CO), 209.2(s, and evaporated to give a colorless liquid (0.913g, 93% crude yield). The
equatorial Mn(CO),), 208.0 (s, axial Mn(CO)), 142.9,134.8,126.3, alcohol was further purified by thin-layer radial chromatography
126.I (s, ipso and para and both C=C), 127.8,125.0(ortho and meta), (Chromatotron Model 7924,Harrison Research, Inc.) with CH2CI2on
66.2 (s, MnCOCH,), 23.6 (s, MnCOCH,CH,), 15.1 (s, CH,). IR silica gel. Yield: 0.615 g (3.49X lo-' mol, 62%). 'H NMR (C6D,):
(CH2C12): 2115 w, 2051 w, 201 I s, 1642 w (acyl) cm-I. Anal. Calcd 6 7.34-7.07(m, 5 H, aromatic), 5.73 (tq, 'JHH= 7 Hz, ,JHH = 1.3 Hz,
for C I ~ H I & V ~ C, ~ : H, 3.56. Found: C, 55.42;H, 3.58.
~ O55.45; I H, C=CH), 3.34(t, J = 6.4 Hz, 2 H, CH,OH), 2.12(q, J = 7 Hz,
(CO)5Mn(CH2CH2CH=C(Ph)CH,). A solution of (CO)SMn- 2 H, C=CHCH2), 1.90(d, J = 1 Hz, 3 H, CH,), 1.47(apparent quintet,
(COCH2CH2CH=C(Ph)CH3) (0.503g, I .37 X IO-, mol) in E t 2 0 (25 J = 7 Hz, 2 H, CH2CH2CH2),0.72(br s, 1 H, OH).
mL) was refluxed for 5.5 h. The solvent was evaporated, and the residue NMR Line Simulation. Line-simulation calculations were carried out
was extracted with hexane and filtered. The hexane was evaporated to on the Aspect 3000 computer of the Bruker NMR spectrometer with use
give a yellow-white solid (0.420g, 90% yield). Sublimation (50"C, IO', of the iterative line-simulation program PANIC. Proton labels are as
Torr) gave a white solid. 'H N M R (CD2C12)6 7.5-7.1(m, 5 H, aro- follows: MnCHAHBCHcHDCHE=CIC(H,),IPh. Chemical shifts (Hz)
matic), 5.90 ( I H, C=CH), 2.57(2H, MnCH2CH2),2.06 (3 H, CH,), are the following: &(HA)333.7,6(HB)334.7,6(Hc) 772.2,6(HD) 769.3,
1 . 1 I (2H, MnCH,); see Figure 2 for spectra. "C{'H) NMR (toluene-d,, b(HE) 1772.2,and 6(HF) 617.7. J H H values (Hz) are the following:
-40 "C): 6 213.8 (s, equatorial MII(CO)~),210.2 (s, axial Mn(CO)), *J(A,B) = 15.4,'J(A,C) = 'J(B,D) = 5.1, ,J(A,D) = 'J(B,C) = 12.0,
35.7 ( s , MnCH2CH2), 15.5 (s, CH,), 5.8 (s, MnCH2), aromatic and 4J(A,E) = 0.3,4J(B,E) = 0.5,2J(C,D) = 11.5,'J(C,E) = 7.0,,J(C,F)
C=C resonances obscured by the toluene solvent peaks. IR (cyclo- = I4D.F) = 0.6,,J(D,E) = 7.6,and ,J(E,F) = 1.3.
hexane): 2105 w, 2006 s, 1989 m cm-'. Anal. Calcd for C I ~ H I ~ M ~ O , : General Procedure for Reactions Carried Out in NMR Tubes. Reac-
C, 56.49;H, 3.85. Found: C, 56.59;H, 3.80. tions between (CO),MnR and HMn(CO),, which were carried out in
Mn2(C0)9(?'-HCOC6H4CH1). @-CH3C6H4)Mn(CO),(0.930g, 3.25 NMR tubes, were prepared by adding a measured quantity of
X IO-' mol) was dissolved in methylcyclopentane ( I O mL), and HMn- (CO),MnR and an internal NMR integration standard (bibenzyl or
(CO), (0.676g, 3.45 X IO-' mol) was added by vacuum transfer. After 1,4-bis(trimethylsilyl)benzene) to an NMR tube in the glovebox. The
32 h at room temperature, the solution was dark wine red with a small NMR tubes were either joined to a stopcock so that they could be sealed
amount of orange precipitate. Cooling to -35 "C produced red-orange off with a flame on the vacuum line or connected to a Teflon valve
crystals, which were collected by filtration and dried under vacuum. directly on the top of the tube ( N M R tubes with J . Young valves pur-
Yield: 1.25g (2.59X IO-] mol, 80%). 'H NMR (C6D6): 6 8.91 (s, chased from Wilmad Glass Co.). The NMR tube was then removed
CHO), 6.93,6.56 (AA'XX', J(apparent) = 8.0 Hz, 4 H, ortho and from the glovebox and attached to a high-vacuum line, and C6D6 was
meta), 1.77(s, CH,). "CI'HJ NMR (toluene-& -40 "C): 6 226.4 (s, added by vacuum transfer. I n some experiments, the height of the so-
2 Mn(CO)), 223.0 (5 Mn(CO)), 216.0 (2 Mn(CO)), 204.5 (aldehyde lution was measured at this point (i.e., prior to addition of HMn(CO)5)
CO). 148.6 (s, ipso), 13 1.8, 130.0 (s. ortho and meta), other aromatic so that the percent volume of HMn(CO)5 could be subsequently deter-
C obscured by toluene solvent resonances, 21.9 (s, CH,). IR (hexane): mined. The volume of the solution was calculated from the height of the
2089 w, 2023 s, 2003 m, 1992 s, 1981 s, 1974 m, 1974 m, 1966 m, 1939 solution in the NMR tube with a published formula.40 The HMn(CO),
w, 1635 w cm-I. UV-vis (cyclohexane):, , A, 340 nm (c = 1.5 X IO4 M-' was then added by vacuum transfer, and the tube was either flame-sealed
cm-I), 470 (5.5 X IO'). Anal. Calcd for C17H8Mn201,:C. 42.35;H , or sealed by closing the Teflon valve. Tubes were generally kept at -196
1.67;Mn. 22.8. Found: C, 42.24;H, 1.60;Mn, 22.5. "C and thawed immediately prior to measuring the initial NMR spec-
Mn2(CO),(q1-CH3CHO).CH,Mn(CO), (0.673g, 3.20X IO-, mol) trum. Spectra were measured over the couse of the reaction and inte-
was dissolved in hexane (18 mL), and HMn(CO), (0.617g, 3.15 X IO-) grated vs the internal standard.
mol) was added by vacuum transfer. After 50 h at room temperature, Kinetics of the Reaction of (CO),MnR' with HMn(CO),. NMR tubes
the solution was dark wine red with a light orange precipitate. The were prepared as described above, with 10-1 I mg of (CO)5MnR' in each
volatiles were removed by evaporation, and the light orange product was experiment. The percent volume of HMn(CO), varied from 9% for
washed with hexane (2 X 5 mL) and dried under vacuum to give a n [HMn(CO),] = 0.535 M to 39% by volume for the kinetic run at (H-
orange powder. Yield: 0.635g (1.56X mol, 50910). 'H NMR Mn(CO),] = 2.6 M . 'The reactions were monitored by ' H NMR at 25
(C6D6): 6 7.91 (br s, 1 H, CHO), 0.84 (br s, 3 H, CHI). The ' H NMR "C. Pseudo-first-order rate constants were determined from the slope
resonances appear at slightly different chemical shifts for the isolated of plots of In ([(CO),MIIR'],/[(CO),M~R']~) vs time. A sample plot
aldehyde complex compared to those of the"same complex prepared in is shown in Figure 4. The ratio of free to complexed aldehyde changed
an NMR tube from (CH,)Mn(CO)5 (-0.3 M) and excess HMn(CO),. as the reaction proceeded (see Figure 5). After the completion of the
When prepared in the NMR tube in concentrated solutions, the reso- kinetics experiments, the tubes wcrc removed from the NMR spectrom-
nances appear at 6 8.1 8 and 6 1.06.IR (hexane): 2092 w, 2024 s. 2005 eter and kept at room temperature i n the dark for 3-5 days. Another
m, 1995 s, 1982 s. 1974 m, 1970 m, 1946 sh w, 1940 w. 1678 w cm-I. ' H N M R spectrum was then taken to determine the yield of Ph(CH,)-
Anal. Calcd for CllH4Mn2Ol,:C. 32.54;H, 0.99. Found: C. 32.90: C=CHCH2CH2CH20H.
H, 1.46. Determination of K , for Eq 6. With usc of the general procedure
Mn2(C0)9(v1-HCOCH2CH2CH=C( Ph)CH,). This aldehyde complex outlined above, (CO),MnR' (10.9mg, 3.2 X IO-, mol) and an internal
was isolated i n 50-70% yield from the ring-opening hydroformylation intcgration standard ( I ,4-bis(trimcthylsilyI)benzene) were added to an
reaction (eq 2) carried out in hexane at 7 OC. Details of this preparation
will bc publishcd scparatcly, including the prccise proccdurcs rcquircd (40) Bryndza, H. E.; Calabrese, J. C.; Marsi, M.; Roe, D. C.; Tam, W.;
for HMn(CO), in order to ensure the reproducibility of the ring-opening Bercaw. J . E. J . Am. Chem. SOC.1986, 108, 4805-4813.
Mn2(CO)9( v i -aldehyde) Complexes J . A m . Chem. SOC.,Vol. 113, No. 5, 1991 1669
N M R tube. C6D6and HMn(CO), (77 mg, 3.9 X IO4 mol) were added Reaction of CH,Mn(CO), with DMn(CO),. With use of the general
by vacuum transfer, giving a solution that had a total volume of 0.49 mL procedure outlined above, CH,Mn(CO), (23.5 mg, 1.12 X IO4 mol) and
and initial concentrations of [(CO),MnR’] = 0.065 M and [HMn(CO),] 1,4-bis(trimethylsilyI)benzene (3.4 mg) were added to an N M R tube.
= 0.80 M. The tube was frozen at -196 ‘C and then thawed and placed C6D6 and DMn(CO), (84% D) were added by vacuum transfer. Initial
in an N M R probe at 8 OC. The approximate pseudo-first-order rate concentrations were [CH,Mn(CO),] = 0.20 M and [DMn(CO),] = 1.0
constant for the reaction was k = 2.1 X IO-, s-I. A plot of [Mn,- M . Comparison of the volume of the tube before and after addition of
(CO),(q’-R’CHO)]/[total aldehyde] similar to that shown in Figure 5 DMn(CO), indicated that the solution was 20% DMn(CO), by volume.
was obtained. The equilibrium constant for eq 6 is Kc4 = ([R’CHOI- After 24 h at room temperature, the solution was dark wine red and ‘ H
[HMn3(CO)1 4 ] ) / [( Mn,(CO),(q’-R’CHO)] [HMn(CO),]). Since the N M R integration of the methyl groups (vs the 1,4-bis(trimethylsilyI)-
stoichiometry of eq 6 requires that [HMn,(CO),,] = [R’CHO] at all benzene internal standard) indicated Mn,(CO),(q’-CH,CDO) (6 0.95,
times, it proved more convenient (and accurate) experimentally to mea- 61% yield), free CH,CDO (6 1.40, 19% yield), and unreacted CH3Mn-
sure the equilibrium constant as K, = [R’CH0l2/([Mn2(CO),($- (CO), (6 0.21,8%). At t = 5 . 5 days, the color of the solution was orange;
R’CHO)] [HMn(CO),]). (Separate measurements with integrated val- CH,CN (7 pL) was added to displace coordinated aldehyde and alcohol,
ues for [HMn,(CO),,] gave similar values of K,. In most experiments, and the solution turned lighter orange. The methyl resonance of CH3-
a large excess of HMn(CO), was used so [HMn(CO),] did not change C D O was observed at 6 1.40, and that of CH3CD20Dwas observed at
appreciably during the course of the reaction and the concentrations of 6 0.95. Singlets at 6 1.43 and 1.12 were observed for the CH, groups of
free and complexed aldehydes were readily measured by ‘HN M R in- Mn3(C0)9(p3-OCD2CH,)2(p2-OCD2CH3). The CH,CDO and
tegration). I n this experiment, the Kc4 determined from 12 data points CH3CD20D/CH3CD20Hwere also identified by GC/MS.
collected during the first half-life of the reaction was equal within ex- Reaction of CD,Mn(CO), with HMn(CO),. With use of a procedure
perimental error to the K , determined from data points taken after 3-5 analogous to that described above, a C6D, solution of CD,Mn(CO), (20.6
half-lives. The average Kcqdetermined at 8 OC was K,, = 1 . 1 ( f 0 . 2 ) X mg, 9.67 X IO-, mol; >99% D; initial concentration 0.16 M) and
10-2. HMn(CO), (initial concentration 1.0 M) was prepared in an N M R tube.
Isotope Effect Determination for the Reaction of (CO),MnR’ with After 24 h, an N M R spectrum of the dark wine red solution indicated
HMn(CO),/DMn(CO),. With use of the general procedure outlined a 1:2.7 ratio of free C D 3 C H 0 (6 9.20, br) to Mn2(CO),(q1-CD,CHO)
above, (CO),MnR’ (9.1 mg, 2.7 X lo-, mol) and an internal integration (6 8.05). After a total of 5.5 days at room temperature in the dark, the
standard ( I ,4-bis(trimethylsiIyI)benzene)were added to an N M R tube. intensity of the resonances due to C D 3 C H 0 and Mn,(CO),(q’-
C6D6,HMn(CO), (72 mg, 3.7 X IO4 mol), and DMn(CO), (69 mg, 84% CD,CHO) had decreased; singlets observed at 6 4.22 and 3.00 are as-
D) were added by vacuum transfer. Taking account of the percent D in signed to Mn,(C0)9(p3-OCH2CD3)~(p~-OCH2CD3). Addition of CH3-
the DMn(CO), and the volume of the the solution, the initial concen- C N (7 pL) caused a slight color change from medium orange to a lighter
trations were determined to be [(CO),MnR’], = 0.05 M, [HMn(CO),], orange. The volatile components were vacuum-transferred to another
= 0.81 M, and [DMn(CO),], = 0.56 M. Three spectra were taken over N M R tube, and the ‘ H N M R spectrum exhibited resonances for CD3-
the course of the reaction (when the reaction was 54, 85, and 100% C H O (6 9.17) and CD,CH,OH (6 3.33, s). The presence of C D 3 C H 0
complete). From each of these spectra, the amount of H in the aldehyde and CD,CH,OH was also confirmed by GC/MS.
C H O position was determined (vs the vinyl H of the aldehyde) for both Reaction of Mn2(CO),(rl’-HCOC6H,CH3) with EtOH and EtOD.
the free and complexed aldehyde. This gave six separate measurements Mn2(CO),(q’-HCOC6H4cH3)(13.5 mg, 2.80 X IO-, mol), internal
of the isotope effect. The average of these six determinations indicated standard (1,4-bis(trimethylsilyI)benzene), and C6D6 were added to a
that k H / k D = 1.04 & 0.09. screw-cap N M R tube. When EtOH (-5.5 equiv) was added, the dark
Reaction of CH3Mn(CO)5 with HMn(CO),. With use the general wine red solution of the aldehyde complex turned to a lighter red-orange
procedure outlined above, CH,Mn(CO), (37.7 mg, 1.79 X IO4 mol) and color and integration of free and complexed alcohol and aldehyde indi-
bibenzyl (9.8 mg, internal migration standard) were added to an N M R cated Kq = 0.4. Resonances for Mn2(C0)9(CH3CH,0H) are as follows:
tube. C6D6 and HMn(CO), were added by vacuum transfer. Initial 6 4.14 ( t , J = 5.3 Hz, I H, OH), 3.00 (apparent quintet, J = 6.6 Hz, 2
concentrations were [CH,Mn(CO),] = 0.35 M and [HMn(CO),] = I .8 H, CH,), 0.70 (t, J = 6.9 Hz, 3 H, CH,). I n a similar experiment with
M. Comparison of the volume of the tube before and after addition of CH3CH20D,resonances assigned to coordinated C H 3 C H 2 0 Dwere ob-
HMn(CO), indicated that the solution was 33% HMn(CO), by volume. served at 6 3.05 (q, J = 7 Hz, 2 H, CH,), 0.76 (t, J = 7 Hz, 3 H, CH,).
After 21 h at room temperature, the solution was dark wine red and ‘ H Preparation of Mn3(CO)9(p3-OEt)2(p2-OEt). This Mn, cluster was
N M R integration indicated Mn,(CO),(q’-CH,CHO) (72% yield), free prepared in 53% yield from the reaction of BrMn(CO), with EtOH and
CHJDO (21% yield), and unreacted CH,Mn(CO), (-1%). After 70 NEt, via the published procedure.I6 ‘ H N M R (C6D6): 6 4.20 (q, J =
h , the yields had decreased to 36% Mn,(CO),($-CH3CHO) and 13% 6.8 Hz, 2 H. p*-OCH,CH,), 2.95 (q, J = 6.8 Hz, 4 H, F~-OCH,CH,),
frec CHJHO. After 7 days, both of these compounds were nearly 1.37 (t, J = 6.8 Hz,3 H, p,-OCH,CH,), 1.07 (t, J = 6.8 Hz, 6 H,
completely consumed and two very broad, overlapping resonances were fi,-OCH,CHj). ‘ H N M R (CDCI,): 6 4.53 (a,, J = 6.9 Hz. 2 H, ~ 2 -
observed at 6 3.62 and 3.33 in about a l:3 intensity ratio. Addition of OCHZCH,), 3.47 (q, J = 6.9 Hz, 4 H.p,-OCH,CH,), 1.61 (t, J = 6.9
CH,CN ( I O pL, 0.4 M) resulted in the coalescence of these resonances Hz, 3 H, p,-OCH,CH,), 1.47 (t, J = 6.9 Hz, 6 H,p,-OCH,CH,). The
to a single broad resonance at 6 3.42. This resonance is assigned to the IR spectrum (hexane) of this authentic material was identical with the
C H 2 group of ethanol; the yield of ethanol was 41%. Further support spectrum of Mn3(CO)9(p3-OEt),(p2-OEt) that was prepared from the
for this assignment comes from the increase in the intensity of this peak reaction of CH,Mn(CO), with HMn(CO),; these observed IR bands
(as well as the peak at 6 I .01 assigned to the methyl group of ethanol) agree ( 1 2 cm-I) with those reported previously.’6
when ethanol (15 p L ) was added. Along with the broad peaks noted
above and assigned to free and coordinated ethanol, two quartets (6 4.25, Acknowledgment. This research was carried o u t a t Rrcokhaven
3.04. J = 6.8 Hz) and accompanying triplets (6 I .43. I . I 6) were also National Laboratory under Contract DE-AC02-76CH0016 with
observed in the reaction of Mn,(CO),(q’-CH,CHO) with HMn(CO),. t h e U S . D e p a r t m e n t of Energy a n d supported by its Division of
These resonances are due to Mn,(CO),(p,-OEt),(p,-OEt). This as-
signment was confirmed by comparison of the IR and ‘ H NMR spectra C h e m i c a l Sciences, Office of Basic Energy Sciences. We
of Mn3(CO)9(p3-OEt),(p,-OEt)from reaction 9 with those of this com- gratefully acknowledge D r . Edward Samsel for preparation of t h e
pound prepared by a known route.16 The 44% yield of this Mn, cluster, P h ( C H 3 ) C = C H C H 2 C H 2 C 0 , H a n d for o t h e r preliminary ex-
together with the 41% yield of EtOH mentioned above, accounts for an periments o n this project. W e thank Drs. M a r k Andrews, George
85% combincd yicld bascd on CH3Mn(CO),. C o u l d , a n d Frederick L e m k e for helpful suggestions.