Oxomolybdenum Chemistry

An Experiment
Charles G. Young
University of Melbourne, Parkville 3052, Australia

Metal oxides are important industrial catalysts (1) and

certain biological systems, notably those containing Mn,
Fe and Mo, exploit 0x0-metal active sites in a wide variety
of catalytic reactions (2). Indeed, the high-valent chemistry of the early and middle transition metals is dominated
by 0x0 complexes (3).Diverse and important, oxomolybdenum chemistry is particularly instructive and relevant in
undergraduate inorganic chemistry (4). I t forms the basis
of this undergraduate experiment.
stabilizes high-valent metThe 0x0 lieand.
, formallv 02-.
al centers by both o-and ;-bask interactions and is susceptible to both nucleo~hilicand electro~hilicattack. Nncleophilic attack by phkphine on a d i o x o - ~ o (center
~ ~ ) leads
to oxygen atom transfer (51, two-electron reduction of molybdenum and concomitant oxidation of phosphorus (eq 1).

[ ~ 0 ~ ' 0+~:PR,
1 ~+
+ [ M O ~ O+ ]OPR,
~~

(1)

In a complementary reaction, oxygen atomdonors such a s

S- andN-oxides, peroxides and dioxygen are capable of oxidizing 0x0-Mo(1V) complexes, thus generating dioxoMo(V1) species (e.g., eq 2). Under suitable conditions,
coupling of reactions 1and 2 permits catalytic oxygen atom
transfer processes to be realized (5).Electrophilic attack
on a n 0x0 group is exemplified by simple protonation, as
shown in eq 3; these reactions do not change the oxidation
state of the molybdenum. I n the absence of other ligands,
protonation is followed by condensation and polyoxomolyhdate formation (4). In the presence of other ligands,
selective replacement of the 0x0 ligands may he promoted
by protonation. Another prevalent reaction in oxomolybdenum chemistry is the comproportionation reaction shown
in eq 4.
Reactions 1 4 are exploited in the synthesis of innumerable Mo complexes (41, account for much of the chemistry
t catalvtic redox
of such comalexes (4). and are i m ~ o r t a nin
reactions s;ch a s those mediated by industrial'oxidation
catalysts (1)and the molybdoenzvmes sulfite oxidase, xanthine oxidase and nitrate reduccase (6). Comproportionation reaction 4 must he sterically prevented in realistic
models of mononuclear oxomolybdenum enzyme centers

(6).
This experiment involves the synthesis and characterization of several oxomolybdenum complexes containing the N,N- diethyldithiocarhamate ligand and the exploration of a n historically important system for catalytic
oxveen atom transfer. (See firmre.) Firstlv. acidification of
a kTxture of ~ 0 0 4 "and N ~ & C N E(prepared
~~
in situ) is
e m ~ l o v e dto svnthesize the octahedral cis-dioxo-Mo(V1)
c0&~1exe i s - ~ o ~ z ( ~ z ~(1)
~ (7).
~ t This
z ) z is converted to
t h e s q u a r e p y r a m i d a l 0x0-Mo(1V) complex

(YI

(81

The chemical reactions involved in this experiment.

MoO(S2CNEtz)z [Redl and the dinuclear poxo-MOW)complex syn-MozOz(p-O)(SzCNEtz)4 [Purple], by reactions
with PPhn- (c.f... ea. 1)(8).These three com~lexesare compon m t s of the now classlc catalytic oxygen :Itom transfer iys:em first d c w r i h d b\. B x r a l and co-workers (9.101. 'l'heir
structures, or thosewofclosely related derivatives, have
been determined by X-ray diffraction (11).Reaction of 1
with hydrochloric acid results in the formation of seven-coordinate,
pentagonal
hipyramidal
cis-merMoOCIz(SzCNEtz)z Eellow] (12). If time permits, t h e
structurally related chiral seven-coordinate complex
MoO(S2)(SzCNEtz)z [Blue] may be prepared and sulfur
atom transfer reactions contrasted with their oxygen atom
counterparts (13).The literature syntheses of all complexes have been simply and successfully modified for the
undergraduate laboratory. Moreover, the experiment may
be tailored to suit the level of student and time available.
Less advanced students may simply be required to perform the syntheses and observe and explain the oxygen
atom transfer chemistry. For more advanced students, the
identity of the compounds can be withheld and, upon provision or collection of analytical and spectroscopic data, the
students may be required to determine the formulae and
structures of the compounds and explain the chemistry.
The experiment is typically performed over a four-hour period with the simultaneous synthesis of P, R and Y. An
Volume 72 Number 8 August 1995

751

additional period i s generally required if B i s to be prepared along with the aforementioned.

The experiment highlights:
1. Avariety of synthetic strategies based on eqs 1 and 2.
2. The study of complexes with a variety of coordination
numbers, geometries, and nuclearities.
3. Analysis of the infrared, 1H NMR and mass spectra of the
complexes.
4. An examination of stoichiametrie and catalytic oxygen
atom transfer reactions.
5. A comparison of simple oxygen atom transfer and sulfur
atom transfer reactions.

C ~ S - ~ ~ ~ - M O ~ % C Z (Y)
~ ((121
S~CNE~~)~

While most syntheses can be performed on a n open

bench, the dispensing of malodorous or toxic substances
such as HNEtz, CSz, concentrated HC1, chlorinated solvents and propylene sulfide should be carried out i n a fume
hood.

NaOH + NaS2CNEt2 + H20

(5)

Success depends on vigorous agitation or magnetic stirring during the addition of the hydrochloric acid. Diethylamine (2.4 mL, 23 mmol) and sodium hydroxide (0.9 g, 23
mmol) are added to water (50 mL) in a 250-mL Erlenmeyer
flask. After stirring for 5 min, the mixture is treated with
carbon disulfide (1.4 mL, 23 mmol), a watchglass is placed
over the top of the flask and the solution is stirred for a
further 10 min. Sodium molybdate(V1) dihydrate (3.5 g,
14.5 mmol) is added to the mixture. which is then treated
dropwise (from a dropping funnel, over about a 10 min period) with a solution of 6 mL of concentrated hvdrochloric
acidin water (100 mL). Vigorous stirring is required during the dropwise addition; the dense yellow-brown product
precipitates. The solid i s isolated by vacuum filtration,
washed well with water (60 mL), ethanol (60 mL), then
ether (60 mL) and dried a t the pump. The crude material
may be employed in the syntheses that follow. The remainder of the sample can be recrystallized by dissolving it in
dichloromethane (15 m u g ) , filtering, and adding ether (20
mL/g) to the clear filtrate. Yield 4.0 g, 85 %.
IR (KBr): MCN) 1510s; v(Ma=Ol 920, 880s cm-'. 'H NMR
(CDCl,, 400 MHz): 6 1.32 (t, 12H, 3~ 7.5 Hz, 4 x CH31,3.80 (q, 8H,
4 x CH,) (fluxional on NMR timescale).

M O ~ O ( S ~ C N(R)
E ~(81
~)~
This compound is moderately air-sensitive and all work
should be nerformed anicklv and efficientlv. I n a small
round-bottomed flask connected with a water or air condenser. a mixture of 1 (1.0 e, 2.3 mmol) and triphenvl. .
phosphine I 1.0g , 3.8 mniol: thc excess alloursthe synthrsii
to be ~ e r t o r m e din air. in I Z d i r h l o n ~ e t h e n~~l )~X"
v ' C , 10
mL) is refluxed for 10-15 min. Ensure that reflux (in a preheated bath) is commenced immediatelv after adding the
solvent to the starting materials. upon-completion of the
reflux pour the reaction mixture, with swirling, into icecold ethanol (50 mL) contained i n a 100-mL Erlenmeyer
flask. Filter the crystals, wash with ethanol, then ether,
and vacuum dry. Yield 0.77 g, 80%.
IR (KBr):v(CN) 1520s; v(Mo=Ol 960s em-'. 'H NMR (CDCI3,
400 MHz):6 1.35(t, 12H,3J7.5 Hz, 4 x CH3),3.87 and 3.93(m, 8H,
'5 15 Hz, 3~ 7.5 Hz, 4 x diastereotapie CH2).

752

Journal of Chemical Education

A solution of 1 (0.5 g, 1.2 mmol) i n dichloromethane (5

mL) is filtered through a fluted filter paper into a 25-mL
Erlenmeyer flask, then the filtrate is treated with a solution of triphenylphosphine (0.16 g, 0.6 mmol) in methanol
(10 mL). The mixture is swirled for a few seconds then left
to stand for 15 min (longer times may be employed if the
flask is tightly stoppered). The purple solid formed is vacuum filtered, washed with methanol a n d dried a t t h e
pump. Yield 0.42 g, 85 %. The true color of the compound is
revealed only when a sample is crushed on a white surface
(e.g., tile or paper).
IR (KBr): v(CN) 1500s;v(Mo=O)940s, 920sh; v(MaOMal750w
em-'.

Experimental Procedure
Preparations

HNEt, + CS,

S ~ ~ - M O ~ ~ O ~ ~ ~ - O )(P)
( S(81
ZCNE~Z)~

Asolution of crude 1(0.5 g, 1.2 mmol) in acetone (35 mL)

i s filtered through a fluted filter paper, then the filtrate is
treated with concentrated hydrochloric acid (2.5 mL, excess) and the mixture stirred for 20 min. The product is
isolated bv filtration. washed with 10 mL of acetone and
0.39 g, 70%. If time permits, large
dried a t t<e pump.
crystals of the product can be obtained by allowing the reaction mixture to stand undisturbed for 2-3 h (or overnight) following the initial mixing of the solutions.

YLI~

IR (KBr): v(CN) 1520s; v(Ma=O)950s em-'. 'H NMR (CDCI3,

400 MHz): 6 1.25 ibr t, 12H, 9 7.5 Hz, 4 x CH3),3.90 (m, 8H, 4 x
diastereotapie CH21.

M O ~ ' O ( S(~S) ~ C N E ~(B)

Z )(131
~
Use a n efficient fume hood when using propylene sulfide
and wash all glassware (with dichloromethane) in a fume
hood, placing the washings into a residue bottle therein. In
a small Erlenmeyer flask, a solution of R (0.25 g, 0.6 mmol)
in dichloromethane (5 mL) i s treated with propylene sulfide (0.25 mL, 3.2 mmol). The flask is capped and the mixture stirred for 1 h (the reaction can be left overnight
.. if
necessnry . Thin-levc.r chn~mat~,grapliv
can be employed
to monitor the forniat~onol'the blue rrrudurt. .\ftrr s t i r r i n ~ ,
the reaction mixture i s loaded onto- the top of a silica gel
(70-230 mesh) column and eluted with dichloromethane.
The blue fraction is collected, evaporated to about 0.5 mL
on a rotary evaporator and triturated with ethanol (15
mL). The solid is collected by vacuum filtration, washed
with ethanol (5 mL) and dried a t the pump.
Sulfur (0.1 g, 3.1 mmol) may be used i n place of propylene sulfide if the reaction is performed for 30 min in refluxing 1,2-dichloroethane (workup a s above).
IR (KBr): v(CN) 1525s, 1495s; v(Ma=O)925s; v(S-S) 550 em-'.
'H NMR iCDC13,400 MHz): 6 1.04, 1.32, 1.36 and 1.37 (4t, 4 x 3H,
3~ 7.5 Hz. 4 x CHd, 3.42 and 3.51 (m, 2H, '5 15 HZ,3~ 7.5 Hz,
diastereotopic CH;), 3.7-4.0 (m, 3 x ZH, 3 x diastereotopic CH21.
Oxygen Atom Transfer Chemistry
Students observe the reactions which take place when 1
is reacted with one-half mole equivalent and excess PPh3
(the preparations of P and R, respectively). With careful
observation of the following test tube experiments, more is
revealed about these and related reactions; careful note
should be taken of the observations (use 1-2 mg1mL solutions of the compounds).
1. Using dichloromethane as solvent, dissolve roughly equal
amounts 1and R in separate test tubes, then mix the two
solutions. Compound P is farmed.
2. Allow a solution of R to stand in air or under a flow of
oxygen gas. Yellow 1is slowly formed.
3. Add a drop or two of hydrogen peroxide solution to a solution of R in dichloromethane, swirl for a minute. Add excess (use a large spatdal PPh3 to the yellow solution

farmed. Repeat. Interconversion of R and 1is effected hefore decomposition takes place.
4. React a solution of R with excess PPh3.
Another observation students should be made aware of
and think about is: When a solution of 1and a 50-fold mo~
the inlar excess of PPh3 is monitored in air by 3 1 NMR,
itial spectrum revealing only the presence of PPh3 i s
slowly replaced by a spectrum consistent with the presence
of only OPPh3. A similar observation results when a solution of 1 and a 50-fold molar excess of both PPh3 and dimethylsulfoxide (MezS=O)is monitored in a sealed tube by
3 1 NMR.
~
Blank experiments show that in the absence of
1,PPh3 is not converted to OPPh3 in the presence of oxygen or MezSO alone.
Analvtical and Swctroscovic Data

[A folder containing analytical and spectral data along

with other material useful in the interpretation of these
data may be obtained upon request from the author. Some
data are summarized after the synthesis of each compound.] From analytical and (simdated) mass spectral
data students are able to determine the empirical and molecular formulae of the compounds. Having established the
formulas, infrared and nuclear magnetic resonance spectra are examined and molecular structures deduced. Infrared spectra exhibit bands due to the dithiocarbamate (typicall v(CN) 1550-1500 cm-'1 and 0x0 (v(Mo=O) 1000-850
.
cm-3 ) hgands
a s well a s co-ligands such as K-0and szZ-

(14). 1H NMR spectra a t 400 MHz highlight the fluxional

behavior of 1, the impact of molecular svmmetrv on spectral patterns' (esp. pkntagonal bipyraiidal complexes Y
(Cd a n d B (Cij) and the diastereotopic nature of the
CHAHBmethylene protons of R, Y and B (131. Arationalization of the chemistry is possible once the compounds
have been characterized.
Literature Cited
1. Sheldon. R. A,; Koehi, J. K. MelalKatalped Oddation NOrgnnic Compounds;Academic: New York. 1981.
2. Frausto da Silva. J. R. R.: Williams. R J. P. The Bioiogiml Chemistry of lhr Elementi;: Clarendon: Oxford. 1991.
3. Wilkinson, 0.;Gillard. R. D.; McCleveny, J. A. Compiehhennua Cooniinnfion Chomiriiy; Pergamon: Oxford. 1987. Volume 3.
4. Detailedacmunts of oromolybdenum chemistry may be found inRef. 3:1aiSykes,A.
G.Chapter36.1,pp 1229.IblGamer,C.O.:Chamoek,J.M.Chspter36.4.pp1329.
(el Sfiehl, E. I. Chapter 36.5, pp 1375.
5 . For a review of oxygen atom transfer reactions see: Holm, R. H. Cham. Re". 1987,
87,1401.
6. (a1 Burpayer, S. J. N.: Stiefel, E. I. J Chem. Edue. 1985.62.943. ibiHolm, R.H.
Cooid. Chem Reu. 1990. 100, 183. icl Enemark. J. H.; Young, C. G. Ad". Inorg.

rham
1-9
".
1.
.
....... .
..
., A.
,.
7. Moore. F. W.: Larson.M. L.Inore. Cham 1967.6998
. .
8. C h e n , ~J.-J.:
.
M e ~ o ~ a lJ.
d ,W.:~ewton,W E. hrorg Chem 1976,15,2612.
9. (a1 Barral, R.: Bocard, C.: Seree de Rah, I.; SaJus, L. 72tmhsdron Lett 1972, 1693.
(bl Balral, R.:B a d C.; Seree de Roch, I.; Sajus, L. Kine'. Coloi. iEngl. Trans.)
1979
l d., .
i?"
.
...
,.
...

10. Reynolds, M.S.:Berg, J.M.; Holm, R. H. Inorg Chem 1984.23,3057.

11. in) Ricard. L : Estienne, J.; Koraglannids. P: Taledano, E:Fiseher, J ; Mitsch1er.A.;
Weirs. R. J. Cnoid. C h i . 1914.3, 277. tbi Berg, J.;Hodgson, K 0.in or^ Chem.
1980,19,2180.
12. Dirand, J.:Rieard. L.;Weirr,R. J. Chem Soc..DoIton P a n s 1976,278.
13. Y m . X F.;Young,C. G A u a r . J. Chem 1991,44.361.
14. Newton. W E.: McDonald, J. W J. las+Commort Mstols 1977.54, 51.

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