Organometallic Chemistry

JHU Course 030.442 Prof. Kenneth D. Karlin Spring, 2010

Kenneth D. Karlin
Department of Chemistry, Johns Hopkins University
karlin@jhu.edu http://www.jhu.edu/~chem/karlin/

Organometallic Chemistry

030.442 Spring 2010 Prof. Kenneth D. Karlin karlin@jhu.edu Class Meetings: TTh, 12:00 1:15 pm ++ Remsen Hall 347

p. 1

Textbook Organometallic Chemistry (2nd Edition) Gary O. Spessard, Gary L. Miessler Oxford University Press Course Construction: Homeworks, Midterm Exam(s), Oral Presentations (Grads) TA: Craig Bettenhausen (bettenhausen@jhu.edu) Course Information: http://www.jhu.edu/~chem/karlin/

Rough Syllabus Most or all of these topics

Introduction, History/Key advances Reaction Types Oxidative Addition Transition Metals, d-electrons Reductive elimination Rule (EAN Rule) Bonding, 18 e Insertion Elimination Nucleophilic/electrophilic Rxs. Ligand Types / Complexes Types of Compounds Catalysis Processes M-carbonyls, M-alkyls/hydrides Wacker oxidation Monsanto acetic acid synthesis M-olens/arenes Hydroformylation M-carbenes (alkylidenes alkylidynes) Polymerization- Olen metathesis Water gas-shift reaction Other Fischer-Tropsch reaction

p. 2

Reaction Examples
Oxidative Addition Reductive Elimination

p. 3

Vaskas complex

Carbonyl Migratory Insertion

CH3Mn(CO)5

CO

CH3CMn(CO)5
O

Reaction of Coordinated Ligands

(Iron pentacarbonyl)

(CO)4FeC O + :OH > (CO)4Fe (CO)4FeH + CO2

O H

>

Reaction Examples - continued

Wacker Oxidation C2H4 (ethylene) + O2 > CH3CH(O) (acetaldehyde)
Pd catalyst, Cu (co-catalyst)

p. 4

Monsanto Acetic Acid Synthesis CH3OH (methanol) + CO > CH3C(O)OH (acetic acid) (Rh catalyst) Ziegler-Natta catalysts Stereoregular polymerization of 1-alkenes (-olens)

1963 Nobel Prize n CH2=CHR > [CH2-CHR]n Catalyst: Ti compounds and organometalllic Al compound (e.g., (C2H5)3Al )

Olen metathesis variety of metal complexes

2005 Nobel Prize Yves Chauvin, Robert H. Grubbs, Richard R. Schrock

p. 5

Organo-transition Metal Chemistry History-Timeline

Main-group Organometallics
1760 - Cacodyl tetramethyldiarsine, from Co-mineral with arsenic 1899 > 1912 Nobel Prize: Grignard reagents (RMgX)
n-Butyl-lithium

1827 Zeises salt - K+ [(C2H4)PtCl3]

Synthesis: PtCl4 + PtCl2 in EtOH, reux, add KCl

Bonding- Dewar-Chatt-Duncanson model

p. 6

Organo-transition Metal Chemistry History-Timeline (cont.)

1863 - 1st metal-carbonyl, [PtCl2(CO)2] 1890 L. Mond, (impure) Ni + xs CO > Ni(CO)4 (highly toxic) 1900 M catalysts; organic hydrogenation (---> food industry, margerine) 1930 Lithium cuprates, Gilman regent, formally R2CuLi+

1951 Ferrocene discovered. 1952 -- Sandwich structure proposed

(Cp)2Fe Cp = cyclopentadienyl anion) (h5-C5H5)2Fe (pentahapto)

Solid-state structure

Ferrocene was rst prepared unintentionally. Pauson and Kealy, cyclopentadieny-MgBr and

FeCl3 (goal was to prepare fulvalene) But, they obtained a light orange powder of "remarkable stability., later accorded to the aromatic character of Cp groups. The sandwich compound structure was described later; this led to new metallocenes chemistry (1973 Nobel prize, Wilkinson & Fischer). The Fe atom is assigned to the +2 oxidation state (Mssbauer spectroscopy). The bonding nature in (Cp)2Fe allows the Cp rings to freely rotate, as observed by NMR spectroscopy and Scanning Tunneling Microscopy. ----> Fluxional behavior. (Note: Fe-C bond distances are 2.04 ).

p. 7

Organo-transition Metal Chemistry History-Timeline (cont.)

1955 - Cotton and Wilkinson (of the Text) discover organometallic-complex uxional behavior (stereochemical non-rigidity)
The capability of a molecule to undergo fast and reversible intramolecular isomerization, the energy barrier to which is lower than that allowing for the preparative isolation of the individual isomers at room temperature. It is conventional to assign to the stereochemically non-rigid systems those compounds whose molecules rearrange rapidly enough to inuence NMR line shapes at temperatures within the practical range (from 100 C to +200 C ) of experimentation. The energy barriers to thus dened rearrangements fall into the range of 5-20 kcal/mol (21-85 kJ/mol).

Aside: Oxidation State 18-electron Rule

p. 8

Fluxional behavior; stereochemical non-rigidity (cont.)

Butadiene iron-tricarbonyl

Xray- 2 COs equiv, one diff., If retained in solution, expect, 2:1 for 13-C NMR. But, see only 1 peak at RT. Cooling causes a change to the 2:1 ratio expected. Two possible explanations: (1)Dissociation and re-association or (2) rotation of the Fe(CO)3 moiety so that COs become equiv. Former seems not right, because for example addition of PPh3 does NOT result in substitution to give (diene)M(CO)2PPh3.
Note: You can substitute PPh3 for CO, but that requires either high T or hv. So, the equivalency of the CO groups is due to rotation without bond rupture, pseudorotation.

13C-NMR

spectra CO region, only

p. 9

Berry Pseudorotation

Pseudorotation: Ligands 2 and 3 move from axial to equatorial positions in the trigonal bipyramid whilst ligands 4 and 5 move from equatorial to axial positions. Ligand 1 does not move and acts as a pivot. At the midway point (transition state) ligands 2,3,4,5 are equivalent, forming the base of a square pyramid. The motion is equivalent to a 90 rotation about the M-L1 axis. Molecular examples could be PF5 or Fe(CO)5.

p. 10

The Berry mechanism, or Berry pseudorotation mechanism, is a type of vibration causing molecules of certain geometries to isomerize by exchanging the two axial ligands for two of the equatorial ones. It is the most widely accepted mechanism for pseudorotation. It most commonly occurs in trigonal bipyramidal molecules, such as PF5, though it can also occur in molecules with a square pyramidal geometry. The process of pseudorotation occurs when the two axial ligands close like a pair of scissors pushing their way in between two of the equatorial groups which scissor out to accommodate them. This forms a square based pyramid where the base is the four interchanging ligands and the tip is the pivot ligand, which has not moved. The two originally equatorial ligands then open out until they are 180 degrees apart, becoming axial groups perpendicular to where the axial groups were before the pseudorotation.

Organo-transition Metal Chemistry History-Timeline (cont.)

page)

p. 11

1961 D. Hodgkin, X-ray structure Coenzyme Vitamin B12 (see other page) Oldest organometallic complex (because biological) (see other

R H H R Catalysis C C C C of 1,2-shifts H H H H (mutases) or (homocysteine) RSH Homocysteine methylation [B12CoIII-CH3]+

Methylmalonyl-CoA > Succinyl-CoA (CoA = coenzyme A)

RSCH3 (methionine) [B12CoI]

1963 - Ziegler/Natta Nobel Prize, polymerization catalysts 1964 - Fischer, 1st Metal-carbene complex

1965 Cyclobutadieneiron tricarbonyl, (C4H4)Fe(CO)3 theory before experiment (C4H4) is anti-aromatic (4 -electrons)
With

-Fe(CO)3,

C4H4 behaves as aromatic

1965 Wilkinson hydrogenation catalyst, Rh(PPh3)3Cl 1971 Monsanto Co. Rh catalyzed acetic acid synthesis

Vitamin B-12 Co-enzyme

Vitamin B-12 is a water soluble vitamin, one of the eight B vitamins. It is normally involved in the metabolism of every cell of the body, especially affecting DNA synthesis and regulation, but also fatty acid synthesis and energy production. Vitamin B-12 is the name for a class of chemically-related compounds, all of which have vitamin activity. It is structurally the most complicated vitamin. A common synthetic form of the vitamin, cyanocobalamin (R = CN), does not occur in nature, but is used in many pharmaceuticals, supplements and as food additive, due to its stability and lower cost. In the body it is converted to the physiological forms, methylcobalamin (R = CH3) and adenosylcobalamin, leaving behind the cyanide.

p.12

5-deoxyadenosyl group

Organo-transition Metal Chemistry History-Timeline (cont.)

1973 Commercial synthesis of L-Dopa (Parkinsons drug) asymmetric catalytic hydrogenation 2001 Nobel Prize catalytic asymmetric synthesis, W. S. Knowles (Monsanto Co.) R. Noyori,, (Nagoya, Japan), K. B. Sharpless (Scripps, USA)

p. 13

1982, 1983 Saturated hydrocarbon oxidative addition, including methane

1983 Agostic interactions (structures)

p. 14

AGOSTIC INTERACTIONS:

Agostic derived from Greek word for "to hold on to oneself C-H bond on a ligand that undergoes an interaction with the metal complex resembles the transition state of an oxidative addition or reductive elimination reaction. Detected by NMR spectroscopy, X-ray diffraction Compound above: MoH = 2.1 angstroms, IR bands were observed at 2704 and 2664 cm1 and the agostic proton was observed at 3.8 ppm. The two hydrogens on the agostic methylene are rapidly switching between terminal and agostic on the NMR time scale.

Organometallic Chemistry Denition: Denition of an organometallic compound

Anything with MR bond R = C, H (hydride) Metal (of course) Periodic Table down & left
electropositive element (easily loses electrons)

p. 15

NOT: Complex which binds ligands via, N, O, S, other M-carboxylates, ethylenediamine, water MX where complex has organometallic behavior, reactivity patterns
e.g., low-valent

Oxidation State

R'

R'' Charge left on central metal as the ligands are removed in their usual closed shell conguration (examples to follow).

dn

for compounds of transition elements N d < (N+1) s or (N+1) p in compounds e.g., 3 d < 4 s or 4 p

d d

n computation very important in transition metal chemistry n zero oxidation state of M in M-complex has a conguration d n where n is the group #.

p. 16

Examples: Mo(CO)6

Mo(0) d

= d 6 (CO, neutral)

HCo(CO)4 H is hydride, H, --> --> Co(I), d n = d 8 Group 5 Group 6 Group 7 V(CO)6 Cr(CO)6 Mn(CO)6+ V(1) Cr(0) Mn(+1) d6 d 6 d 6
Isoelectronic and isostructural compounds (importance of d n) Effective Atomic # Rule; 18-Electron Rule (Noble gas formalism) # of electrons in next inert gas = # Metal valence electrons + (sigma) electrons from ligands
Rule: For diamagnetic (spin-paired) mononuclear complexes in organotransition metal compounds, one never exceeds the E.A.N.

Cr(CO)6 (CO)6

Cr ---> 6 electrons e - pairs from 6 ligands 12 electrons > to [Ar] conguration 18 electrons (will see more in M.O. diagram)

d6

p. 17

Consequence of EAN Rule: leads to prediction of maximum in coordination # Max coordination # = (18 n) / 2 n is from d n . d n 10 8 6 4 2 0 Max Coord # 4 5 6 7 8 9
Change in 2-electrons results in change of only one in Coord. # Any Coord. # less than Max # ---> coordinatively unsaturated Fe(CO)42
2e +CO 2e CO

Fe(CO)5

18 e 18 e Fe(2) Fe(0) d 10 d 8 4-coord 5-coord both Coord. Saturated

p. 18

[ReH9]2

e.g., as Ba2+ salt

Re(VII), (Mn,Tc, Re triad)

d 0, 9 hydride ligands; CN = 9
Geometry: Face capped trigonal prism

A compound not obeying an rules

Iron-carbonyl carbide

Fe5(CO)15C

p. 19

Eighteen-Electron Rule - Examples

Co(NH3)63+ Cr(CO)6 Obey 18-electron rule for different reasons

Carbonyl Compounds in Metal-Metal Bonded Complexes less straightforward Fe2(CO)9 [-Cp)Cr(CO)3]2 Co2(CO)8
(2 isomers)

p. 20

d6 Octahedral
M+ M+

maximum of 6 coordinate
eg o
sixpointcharges sphericallydistributed

Freeion spherical

t2g
octahedral ligand9ield

M+ M+
Freeion spherical fourpointcharges sphericallydistributed

t2 t e
tetrahedral ligand9ield

p. 21

Picture of Octahedral Complex Various representations

(ignore s orbital

lowercaselettersfor orbital dz2,dx2-y2(e2g) (destabilized) spherical 9ieldof6 charges 10Dqoro dxy,dxz,dyz(t2g) (stabilized)

Oh

p. 22

The ve d-orbitals form a set of two bonding molecular orbitals (eg set with the dz2 and the dx2-y2), and a set of three non-bonding orbitals (t2g set with the dxy, dxz, and the dyz orbitals).
eg orbitals point at ligands (antibonding) appropriate symmetry for -bonds to ligands -bonds will be six d2sp3 hybrids ndz2, ndx2-y2, (n+1)s, (n+1)px,py,pz t2g orbital set left as non-bonding

p. 23

p. 24

Standard MO diagram for Octahedral ML6 complexes with -donor ligands e.g., [Co(NH3)6]3+ (18 e) e.g., W(Me)6 (12 e)

Case I
Electron-conguration unrelated to 18-Rule 1st Row-Complexes with weak ligands

o small or relatively small, eg* only weakly antibonding

No restriction on # of d-electrons 12 to 22 electrons

p. 25

Case II Compounds which follow rule insofar as they

p. 26

never exceed the 18-e rule Metal in high oxidation state o is large(r) (for a given ligand) radius is small -> ligands approach closely > stronger bonding 2nd or 3rd Row Metal - 4d, 5d o is large(er) (for a given ligand); d-orbitals larger, more diffuse.
Complex
ZrF62 ZrF73 Zr(C2O4)44 WCl6 WCl6 WCl62 TcF62

d n
0 0 0 0 1 2 3

Total e Complex
12 14 16 12 13 14 15

d n

Total e
4 1 2 4 5 6 8 16 17 18 16 17 18 16

OsCl62 W(CN)83 W(CN)64 PtF6 PtF6 PtF62 PtCl42

Less than 18 e, but rarely exceed 18 e

p. 27

Similar Result if ligands are high in Spectrochemical Series e.g., CN o is larger V(CN)63 Cr(CN)63 Mn(CN)63 Fe(CN)63 Fe(CN)63 Co(CN)63

d2 d3 d4 d5 d6 d6

Less than or equal to 6 d-electrons eg* not occupied

however Co(II) d7 > Co(CN)53 Ni(II) d8 > Ni(CN)42 and Ni(CN)53

Can have less than maximum # of non-bonding (t2g) electrons, because they are nonbonding. Addition or removal of e has little effect on complex stability

o can get (or is) very small with -donor ligands

F example (could be Cl, H2O, OH, etc.) a) Filled p-orbitals are the only orbitals capable of -interactions i) 1 lone pair used in -bonding ii) Other lone pairs -bond b) The lled p-orbitals are lower in energy than the metal t2g set c) Bonding Interaction i. 3 new bonding MOs lled by Fluorine electrons ii. 3 new antibonding MOs form t2g* set contain d-electrons iii. o is decreased (weak eld) d) Ligand to metal (L M) -bonding i. Weak eld, -donors: F, Cl, H2O ii. Favors high spin complexes

p. 28

p. 29

Metal Orbital s T1u 4p

Molecular Orbitals focuson thispart only

Ligand Orbitals bothsetsofd orbitalsare drivenin energydueto lowerlying ligandorbitals T1g,T2g T1u,T2u orbitals px,py

A1g

4s

Eg T2g

eg (*) t2g(*)

3d t2g ()

A1g

eg()

T1u orbital E pz
g

p. 30

Have discussed -donor and -donor now -acceptor eg(*)

antibonding

eg(*) o o o

eg(*)

t2g()
MLbonding

t2g(n.b.)
nonbonding

t2g(*)
bothare antibonding

-donor acceptor
largestseparation betweensetsofdorbitals intermediate separation

-donor
smallestseparation

Metal Orbitals
(only consider the d orbitals 4s and 4p orbitals not included in the analysis)

Molecular Orbitals Ligand Orbitals t2g(*) T1g, T2g T1u, T2u

Mo(CO)6

p. 31

CASE III

eg (* M-L) Eg T2g

*orbitals on CO L high in spectrochemical series: (6 x 2 each orthogonal) CO, NO, CN, PR3, CNR

-acid ligands -acceptors

o
4d

t2g ()

orbitals on CO (6 x 1 each) A1g Orbitals on M used in such -bonding T1u are just those which are non-bonding Eg

Can form strong -bonds 18 e rule followed rigorously

Result: Increase in o
Imperative to not Have electrons in eg* orbitals

eg (M-L)

Want to maximize occupation of t2g because they are stabilizing

p. 32

p. 33

Implications of 18e Rule for Complexes with -accepting ligands In octahedral geometry almost always have 6 d-electrons 12 electrons from ligands Other cases: # d-electrons and coordination # complementary

Coordination # exactly determined by electron-conguration and vice-versa

BrMn(CO)5 (d ?) (see previous notes) I2Fe(CO)4 (d ?) Fe(CO)5 (d ?) All 18-electron Ni(PF3)4 (d ?)

When M has odd electron > metal-metal bond (often bridging COs) Mn2(CO)10 Co2(CO)8 Some 17 electron species known: V(CO)6 d 5 Mo(CO)2(diphos)2]+ d 5

See MO diagram: Want to ll stable MOs there is a large gap to LUMO

p. 34

Major Exception: d 8 square-planar complexes

As one goes across periodic table, d and p orbital energy Level splitting gets larger hard to use p orbitals for -bonding Common to have 4-coordinate SP complexes dsp2 hybridization
dx2-y2 e g
Which d-orbitals?

o t2g
ML6 ML4

dxy
dz2 dxz dyz (degenerate )

Common for:
Rh(I), Ir(I) Pd(II), Pt(II)

Rationalize d-orbital splittings look at d-orbital pictures/axes

p. 35

p. 36

Again, examples of complexes:

dn
d10 d10 d10 d8 d8 d4 d2 d0

C.N. 4 3 2 5 4 7 8 9

Coord. Geom. Td

Example(s) Ni(CO)4, Cu(py)41+ Pt(PPh3)3

Trig.planar Linear TBP

(PPh3)AuX, Cu(py)2+ Fe(PF3)5

(square) planar capped octahedral sq. antiprism

Rh(PPh3)2(CO)Cl (trans) Mo(CO)5X2

ReH5(PMePh2)3, Mo(CN)84 [ReH9]2

tricapped trig. prism

D3h symmetry

p. 37

LIGANDS in Organometallic Chemistry: Ligands,

X Ar CO R 2N SnCl3 RC(O) (acyl)

charge,

coordination # (i.e., denticity)

CH3 (alkyl, peruoroalkyl) R2P

H (hydride)

R3E (E = P, As, Sb, N)

RNC (isonitrile, isocyanide) N2

R2C (cabenoid, carbene) R2C2 (acetylene)

C2H4 (olen, alkene) C3H5

C4H4 (cyclobutadiene) benzene (arenes)

(-allyl)

CH=CH-CH2 (-allyl) -C7H7 (tropylium) NO (nitrosyl)

-C5H5 (-Cp)

-C3H3 (cyclopropenium, +) ArN2+ (diazonium)

O (O-atom; oxide)

p. 38

Carbon Monoxide exceedingly important ligand

CO-derivatives known for all transition metals Structurally interesting, important industrially, catalytic Rxs Source of pure metal: Ni (Mond); Fe contaminated with Cu, purify via Fe(CO)5 Fe & Ni only metals that directly react with CO Source of oxygen in organics: RC(O)H, RC(O)OH, esters
Processes: hydroformylation, MeOH > acetic acid double insertion into olens, hydroquinone synthesis (acetylene + CO; Ru catalyst), acrylic acid synthesis (acetylene, CO, Ni catalyst) Fischer Tropsch Rx: CO + H2 > > CnH2n+2 + H2O Most of these involve CO insertion

Metal-Carbonyl Synthesis:

p. 39

Reduction of available (in our O2-environment) metal salts, e.g., MX2, MX3, other (e.g., carbonates) M-carbonyls generally in low-valent oxidation states > Reductive Carbonylation
Reductants: CO itself ( > CO2), H2, Na-dithionite Some Reactions: WMe6 + xs CO > W(CO)6 + NiO + H2 (400 C) + CO > Ni(CO)4 3 Me2CO

Re2O7 + xs CO > (OC)5ReRe(CO)5 + 7 CO2

Cl acceptor/reductant RhCl3 + CO + pressure + (Cu, Ag, Cd, Zn) > Rh4(CO)12 or Rh6(CO)16

Structures Possible: X-ray diffraction, Infrared spectroscopy

Ni(CO)4 Td 2058 cm1 Fe(CO)5 M(CO)6 D3h Oh 2013, 2034 cm1 2000 cm1

p. 40

H3BCO = 2164 cm1 no backbonding possible

13C

NMR spectroscopy of M-CO fragments: 180 250 ppm Useful to use 13C enriched carbon monoxide

Can be useful to observed coupling to other spin active nuclei, e.g., 103Rh or 13P

Metal-Carbonyl Structures (cont.):

Polynuclear Metal-Carbonyls

p. 41

p. 42

p. 43

p. 44

p. 45

The backbonding between the metal and the CO ligand, where the metal donates electron density to the CO ligand forms a dynamic synergism between the metal and ligand, which gives unusual stability to these compounds.

Valence Bond formalism: MC

:
:

O:

M=C=O

p. 46

CO stretching frequencies, (C-O)

Put more electron density on metal by charge by ligands which cannot -accept
Remaining COs have to take up the charge (e-density) on the metal See effects on (C-O). Ni(CO)4 [Co(CO)4] Fe(CO)42 2057 cm1 1886 cm1 1786 cm1 > > more ve charge Mn(dien)(CO)3+ Cr(dien)(CO)3 2020, 1900 cm1 ~1900, 1760 cm1 (dien not -acceptor)
~

p. 47

Reactions of Metal-Carbonyl Complexes

Substitution of CO: PX3, PR3, P(OR)3, SR2, NR3, pyridine, OR2, RNC, RCN, olens, NO Examples: Fe(CO)5 + 2 L (or L2) heat or hv> [Fe(CO)3L2] + 2 CO Mo(CO)6 + cycloheptatriene heat or hv> [Mo(cht)(CO)3] + 3 CO Cr(CO)6 + arene heat or hv> [Cr(arene)(CO)3] + 3 CO

Fe(CO)5 + 2 HC=CH
Mn2(CO)10 + Br2 2 PtCl2 + 2 CO

L = PPh3 (trans) heat or hv> [Fe(CO)3(C5H4O)] + CO

O

Oxidation Carbonyl Halides

heat > Mn(CO)5Br heat > [FeCp*(CO)2Br] (2-Cl)2 > [Pt(CO)(Cl2]2 [FeCp*(CO)2]2 + Br2

Fe CO CO

CO

p. 48

Reactions of Metal-Carbonyl Complexes (cont.)

Nucleophilic Attack Reactions with bases Previous Fe(CO)5 + hydroxide
+ PF6 Na+BH4
THF 80 C H H

OC

Fe
CO

+ CO

OC

Fe
CO

C O

OC

Fe
CO

Fischer type M-carbene

O M(CO)n + R3N+O > (CO)n1M C

Use: liberate M(CO)3 groups; or oxidize M

> M(CO)n1 + R3N + CO2 ON+R3

Fe2(CO)9 + 4 OH > Fe2(CO)82 Cr(CO)6 Cr(CO)6 + 3 KOH + BH4 > KHCr(CO)5 + K2CO3 + H2O > [(CO)5CrHCr(CO)5]

p. 49

Reactions of Metal-Carbonyl Complexes (cont.) Alkyl Metal Carbonyls NaMn(CO)5 + CH3X NaMn(CO)5 + RC(O)Cl > Mn(CO)5CH3 > Mn(CO)5C(O)R

NaCo(CO)4 + (C2F5C(O))2O (anhydride) > Co(CO)4C(O)C2F5 +

Metal-Olen Complexes
Zeises Salt, Pt-olen complex Ag-(triate) + C2H4 > [PtCl4]2 + C2H4 > [(C2H4)Ag-OSO2CF3] [PtCl3(C2H4)] + Cl > [Fp-CH2-CH=CH2]+ > [Fp-CH2-CH=CH2]+ [ (Cp)FeI(CO)2 or (Cp)FeII(CO)2+ ]

FeCp(CO)2I + C2H4 + AgBF4 > [FeCp(CO)2(C2H4)]BF4 + AgI Fp-CH2-CH=CH2 + H+ Fp-CHMe2 + Ph3C+BF4

Fp = (Cp)Fe(CO)2

p. 50

Dewar-Chatt-Duncanson model for M-Olen Bonding

Not unlike M-CO bonding and * alkene orbitals

Proper symmetry; good overlap

-Bond olen + empty d-orbital bond *olen + lled d-orbital

Overall double-bond character
M-olen bonding reduces CC bond-strength

p. 51

(2-C70)Ir(X)(CO)(PPh3)2 C60 - Buckminsterfullerene Buckyballs (Soccer-ball 6- and 5-membered rings) Fullerenes Buckyferrocene

Olen -donation to M, AND -donation to * by metal leads to reduction in CC bond strength.

p. 52

Also, for longer CC distances, olen is no longer planar. can regard metal-olen as a metallacyclopropane (sp3 carbons)
Keq > M-olen + L ML + olen < Studied with Pd(II), Ni(0), Rh(I) Keq (M-olen bond-strength) smaller for sterically hindered olens Keq increased by e -withdrawing substituents (-CN, -carboxyl) Keq decreased by e -donating substituents

Back donation from M into olen *-orbital; predominant in M-olen bonding.

Ni(0) d10 olen cannot donate to the metal

Electronic effect less pronounced with metal with less d e -density Ni(0) > Fe(0) > Rh(I) > Pt(II)

p. 53

Also follow by IR spectroscopy: Ethylene, 1623 cm1; Zeises salt, 1516 cm1

Olen coordination tendencies:

Tend to be perpendicular to plane of Square-Planar Complexes

p. 54

In the plane, for trigonal or TBP compounds (Not relevant for octahedral complexes) In solution, olens are not in xed orientations olens rotate (Cp)Rh(C2H4)2 20 C Cp : inner : outer inner and outer Hs = 5 : 4 : 4 i o RT two C2H4 peaks strongly broadened non-equiv Hs exchange at rate intermediate on NMR time scale + 57 C two C2H4 peaks coalesce to one

(Cp)Rh

Exchange fast. NMR cannot distinguish between non-equiv Hs

Cp remains singlet throughout whole T range

Two modes for rotation consistent with NMR spectroscopic data

C C

p. 55

M
C
ON OC PPh3
H'' H'

M
C

Propeller like movement

Os
PPh3

H''

H s are equiv to each other; same with H s but H s are different from H s

H'

Rotation about CC axis would not change situation Propeller movement would exchange non-equiv hydrogens NMR spectroscopy shows two separate peaks at 90 C they coalesce at 65 C > Propeller like movement is operative

Measured barrier to rotation ~ 50-60 kJ/mole for C2H4 No rotation for CF2=CF2 and (NC)2C=C(CN)2 Stronger -bonding restricts rotation

p. 56

Olen metal complexes have a considerable use in organic synthesis Metal alters chemical behavior of olens Metal can activate, deactivate or protect double bond for electrophilic or nucleophilic attack Resolve optical or geometric isomers
direct stereospecic attack aromatic or de-aromatize appropriate systems

Can effect olen metathesis reactions - polymerizations

Example O Cp OC C Fe Fe CO Cp C O
2 HBF4 Et2O

(CO)2CpFeCl + or (CO)2CpFe

THF 0C to 25 C 30 min

Cp(CO)2Fe

[Cp(CO)2Fe
90 %

]+ BF4

NaI acetone

olefin liberated

Use method to reduce epoxides stereospecically to olens with retention of conguration

Another Important Reaction of Olens Wacker Process Hoechst-Wacker Process

Ethylene Oxidation - German Invention

p. 57

1st Homogeneous Catalytic Process with organometallic (R-Pd) compound used on an industrial scale (related to hydroformylation)
Net Reactions: [PdCl4]2 + C2H4 + H2O > CH3CHO + Pd + 2HCl + 2Cl Pd + 2CuCl2 + 2Cl > [PdCl4]2 + 2CuCl

2CuCl + O2 + 2HCl > 2CuCl2 + H2O ==============================================

C2H4 + O2

> CH3CHO

p. 58

p. 59

p. 60

Mechanism summary
Several interesting key points: (1)there is no H/D exchange seen in this reaction. Reaction runs with C2D4 in water generate CD3CDO, and runs with C2H4 in D2O generate CH3CHO. Thus, keto-enol tautomerization is not a possible mechanistic step. (2) There is a negligible kinetic isotope effect with fully deuterated reactants (k H/k D=1.07). Hence, it is inferred that hydride transfer is not a rate-determining step. (3) a signicant competitive isotope effect with C2H2D2, (k H/k D= ~1.9), suggests that the rate determining step should be prior to oxidized product formation. The bulk of mechanistic studies on the Wacker Process debated whether nucleophilic attack occurred via an external (anti-addition) pathway or via an internal (syn-addition) pathway. In summary, it was determined that syn-addition occurs under lowchloride reaction concentrations (< 1 mol/L, industrial process conditions), while anti-addition occurs under high-chloride (> 3 mol/L) reaction concentrations. However, the exact pathway and the reason for this switching of pathways is still unknown.

p. 61

Another key step in the Wacker process is the migration of the hydrogen from oxygen to chlorine and formation of the C-O double bond. This step is generally regarded to proceed through a so-called -hydride elimination with a fourmembered cyclic transition state:

One in silico study[JACS,2006] argues that the transition state for this reaction step is unfavorable (activation energy 36.6 kcal/mol) and proposes an alternative reductive elimination reaction mechanism in which the proton directly attaches itself to chlorine with an activation energy of 18.8 kcal/mol. The proposed reaction step gets assistance from a water molecule acting as a catalyst. Pd(0) Reoxidation Must be complicated

p. 62

This and the next 5 slides are due to Darren Achey and Byron Farnum
Feb09

Shows only Syn mechanism - Nucleophilic attack by OH- ligand

p. 63

Indicates Syn and Anti mechanisms dependence on Cl- concentration

p. 64 Beyramabadi, S. A.; Eshtiagh-Hosseini, H.; Housaindokht, M. R.; Morsali, A.; Organometallics, 2008, 27, 72-79.

- Water-Chain mechanism - Compared Syn vs. Anti mechanisms for rate determining step - All DFT calculations - Accounted for kinetic isotope effect data for O-D vs O-H bond breaking

Syn additi on

Anti additi on

Syn

p. 65

Transition State

Syn-Product

Anti
Lower Activation Barrier Concluded to be the mechanism of ratedetermining step

p. 66

Transition State

Anti-Product

p. 67

Kieth, J. A.; Nielsen, R. J.; Oxgaard, J.; Goddard, W. A.; Henry, P. M.; Organometallics, Feb. 2009

- Rebuked the article by Beyramabadi et. al.

- Emphasized the well established nature of the syn mechanism at low [Cl-] (Standard Conditions) Mech depends highly on [Cl-] and [CuCl2] LL syn mechanism HL Isomerization HH anti mechanism w/ chlorohydrin products

Allyl Ligand Organometallic Complexes

p. 68

unidentate 2-e anionic ligand rarely observed form [CH2=CHCH2Co(CN)5]3 [CH2=CHCH2Mn(CO)5] CC stretch ~ 1620 cm1

alkyl + neutral alkene (2-e )> bidentate most common structure behaves as delocalized -system 3 (4) electrons now valence electrons

[(3-C3H5)PdCl]2 [(-C3H5)PdCl]2

C-C-C ~ 120 (sp2). CC(observed) = 1.40-1.43 ; CC = 1.54 ; C=C = 1.34

Allyl Ligand-M Complexes (continued)

p. 69

[(h3-C3H5)PdCl]2 approximately square-planar (allyl as bidentate) 16-electron system Pd(II), d8, 2 Cls (4 e), allyl is 2 e) (can think about allyl as 3e)
Metal interaction with allyl 3: Always M-to-allyl ligand Can be M-to-L (L-anion) or L-to-M (allyl-cation) Maximize bonding for allyl 2: want terminal Cs in the PdCl2Pd plane. So Allyl plane tilts wrt PdCl2Pd plane from 90 to ~ 110 (central C bent away); moves terminal Cs closer to M

Always Ligand to M. To maximize bonding: PdCl2Pd plane cuts -allyl skeleton~ 2/3 of the distance (center of gravity) from the central C-atom towards the terminal Cs

Allyl Ligand-M Complexes (continued)

p. 70

Tilted allyl group: Organometallics 1985, 4, 285: Neutron diffraction structure

(able to locate Hs) of a Ni-allyl complex. Hmeso and Hsyn are bent towards M (7 and 13 from planar); Hanti are bent 31 away. (D.Astruc text says opposite) Typical static 1H-NMR of trihapto allyl: Hanti at 1 - 3 ppm, Hsyn at 2 - 5 ppm and Hmeso at4 - 6.5 ppm. There is no syn-anti proton-proton coupling. In the 13C-NMR, terminal Cs at 80 - 90 ppm; Central C, 110-130 ppm. Allyl ligands can be uxional on the NMR time scale; see exchange of Hs.

Allyl Ligand-M Complexes (continued)

Syntheses of Allyl-Metal complexes

p. 71

From alkene-complex, H-attack on the metal

Overall 1,3-hydrogen shift

Nucleophilic (electrophilic) substitution using allylic substrate

Oxidative addition of allylic substrate to low-valent metal

Protonation or insertion of a 1,3-diene complex

Allyl Ligand-M Complexes (continued)

p. 72

Allyl-M (-to-; 3-to-1) interconversions important to catalysis/synthesis, as a way to create a vacent coordination site and a way to exert uxional behavior

With excess of PPh3, can observe 1-intermediate by IR spectroscopy 1600-1650 cm1 [Mn(CO)5] + C3H5Cl > (1-C3H5)Mn(CO)5 or h > (3-C3H5)Mn(CO)4 + CO

18-electron species

Allyl Ligand-M Complexes (continued)

Some reactions:

p. 73

Nucleophilic attack: can be stereoselective maybe useful

Insertion reaction

Reductive elimination

Digression A Metallocene of a Different Kind

Uranocene Bis(cyclooctatetraene-dianion)-uranium
Considerations of Aromaticity

p. 74

METAL HYDRIDE COMPLEXES

Important class of compounds
Unstable

p. 75

(relate to M-olen, M-R compounds)

Hydrogenation (stereospecic), hydrogen storage (H2 economy), catalysis

hydrides discovered in 1930s

H2Fe(CO)4,

HCo(CO)4

not understood

1957 breakthrough, J. Chatt (UK)

trans H-Pt(Cl)(PEt3)2
>

discovered by accident, found good prep later

cis-PtCl2(PEt3)2 + N2H4

trans H-Pt(Cl)(PEt3)2 + N2
could be sublimed

strong, sharp Pt-H stretch in infrared spectrum

conrmed by replacement by D

Later, an X-ray structure was obtained, > normal Pt(II) complex

Using M-H stretch, trans H-Pt(Cl)(PEt3)2 used to measure trans effect
conrmed later via studies on actual relative rates of substitution (will discuss)

Metal-Hydride Complexes (continued)

IR/Raman Spectroscopy
more intense than (C-H), ~ 3000 cm1

p. 76

Terminal MH (M-H) 1900 300 cm1

weaker than (C-O), (N-N), (N-C), RNC

Bridging MH 1000 300 cm1

(broad; v1/2 ~ 100 cm1)

Metal-Hydride Complexes (continued)

Aspects of Bonding

p. 77

Metal-Hydride Complexes (continued)

p. 78

Problem: Given a complex formulated as Ru(H)(CO)(Cl)(PPh3)3 IR bands are observed at 2020 cm1 and 1933 cm1. How can you assign the bands either to the RuH or C-O stretching frequencies? MHterminal and MCO terminal IR stretches are in similar regions of spectrum. Thus, cannot assign directly. A solution would be to prepare Ru(D)(CO)(Cl)(PPh3)3 or Ru(H)(13CO)(Cl)(PPh3)3, because IR bands would undergo an isotope shift. Heavy isotope substitution reduces frequency of corresponding vibration; reduced mass, , in Hookes Law, increases {Force constant k doesnt change; bond strengths change little with isotope
substitution.}

Hookes Law:

Metal-Hydride Complexes (continued)

p. 79

1 / 2
For vibration at 2000 cm1:

2 / 1

1/2

Ru-D / Ru-H = Ru-H / Ru-H

1/2

~ 0.71

2000 cm1 x (0.71) = 1420 cm1

For Ru(D)(CO)(Cl)(PPh3)3: Should observe RuD at ~1420 cm1

(13C16O) / (12C16O) = 0.978 For a Metal-Carbonyl at: (12O16O) = 2000 cm1

(13CO) ~ 44 cm1

(18O18O) / (16O16O) = 0.9 For a Metal-Peroxide: (16O16O) ~ 800 cm1

(18O2) ~ 48 cm1

p. 80

Metal-Hydride Complexes (continued)

NMR spectroscopy. high elds, delta () 15-30 ppm relative to TMS along with coupling constants (e.g., JP,H) e.g., distinguish cis vs. trans. useful for sterochemical analysis. Other book: The chemical shift range for hydrides is approximately +25 to 60 ppm. The downeld shifts are most common in d0, d10 and early transition metal cases whereas those with other dn counts and late transition metals tend to be upeld of zero. Coupling to other spin active nuclei such as 31P often makes structural assignments unambiguous. Xray diffraction: near other heavy atoms, position often inferred Other ligands bend towards position of hydrogen, because it is small Neutron diffraction; nding of an atom proportional to Z (X-ray, it is Z2) HMn(CO)5 Neutron diffraction study) MnH = 1.6 , which equals sum of the covalent radii.

TRANS EFFECT (INFLUENCE) in INORGANIC CHEMISTRY

p. 81

Trans effect (inuence) - trans effect is the labilization of ligands trans to certain other ligands, which can thus be regarded as trans directing ligand. It is attributed to electronic effects and it is most notable in square planar complexes, In addition to this kinetic trans effect, trans ligands also have an inuence on the ground state of the molecule, notably on bond lengths and stability Some authors prefer the term trans inuence to distinguish it from the kinetic effect, while others use more specic terms such as structural trans effect (i.e., elongated trans M-L distances) or thermodynamic trans effect. The intensity of the trans effect (as measured by the increase in rate of substitution of the trans ligand) follows this sequence: F, H2O, OH < NH3 < py < Cl < Br < I, SCN, NO2, SC(NH2)2, Ph < SO32 < PR3, AsR3, SR2, CH3 < H, NO, CO, CN, C2H4
Established by substitution kinetic measurements, MH stretch (as mentioned above), or other observations

p. 82

Classic example of the trans effect: the synthesis of cis-platin. Starting from PtCl42, the rst NH3 ligand is added to any of the four equivalent positions at random, but the second NH3 is added cis to the rst one, because Cl has a larger trans effect than NH3. If, on the other hand, one starts from Pt(NH3)42+, the trans product is obtained instead.

Cl

Cl

2 + NH3 Cl

Cl

NH3

1 + NH3 Cl

Cl

NH3

PtII
Cl H3N Cl NH3 2+

PtII
Cl H3N PtII H3N NH3 Cl Cl 1+

PtII
Cl
Cis

NH3 Cl

PtII
H3N NH3

Cl

+ Cl NH3

H3N

NH3

PtII
Cl NH3 Trans

Metal-Hydride Complexes (continued)

p. 83

In hydrido carbonyls, get mixing of (M-CO) and (M-H) modes, especially when CO and H are trans. So deuterate to shift M-D to lower energy and separate out (and less mode mixing).

Metal-Hydride Complexes More Syntheses by Protonation

[Cp2Re] + H+ > HCp2Re
H

p. 84

+
H L Cl

HIr(CO)L3 +

HCl

> L
OC

Mn L

+
Fe
+ H+ >

Fe H

Mn(CO)5 Ni{P(OEt)3}4

+ H+ H+

HMn(CO)5 Ni(H){P(OEt)3}4

p. 85

Metal-Dihydrogen (H2) Complexes

Figure:
ORTEP Drawing Neutron diffraction study, 30 K W(CO)3(PnPr)3)2(2-H2) Intact HH bond Elongated (by ~ 20 %) to 0.82(1)
(lower PR3 disordered)

Metal-Dihydrogen (H2) Complexes (continued)

H LnM H LnM H dihydrogen complex H LnM H dihydride complex H

p. 86

Elongated HH bond: H2 is not physisorbed but chemisorbed H2 bond activated toward breaking

This initially enigmatic Interaction lies at the heart of all Interactions of sigma bonds XY with metals (G.Kubas)

p. 87

Metal-Dihydrogen (H2) Complexes (continued)

H2-binding is reversible (to this analogue with P(Cy)3) relevant to new materials for hydrogen storage ?

Metal-Dihydrogen (H2) Complexes (continued)

p. 88

p. 89

Metal-Dihydrogen (H2) Complexes (continued)

Metal-Dihydrogen (H2) Complexes (Syntheses)

p. 90

Metal-Dihydrogen (H2) Complexes > Hydrides

p. 91

M-H2 complexes also called non-classical hydrides

Metal-Dihydrogen (H2) Complexes (HH bonding / NMR)

p. 92

Solution 1H NMR spectra of 2-H2 ligands normally give broad uncoupled signals throughout a large range of chemical shifts (2.5 to 31 ppm) that can overlap with those for classical hydrides. NMR can be used to determine dHH in solution by two different techniques involving measurement of either JHD or relaxation time, T1. JHD for the HD isotopomer of an H2 complex is the premier diagnostic for H2 versus hydride coordination. The 1H-NMR signal for an HD complex becomes a 1:1:1 triplet (D has I = 1 : (2I + 1) with a much narrower line width and is direct proof of the existence of an H2 ligand, since classical hydrides do not show signicant JHD because no residual HD bond is present. JHD for HD gas is 43 Hz, the maximum value (dHD ) 0.74 ), and lower values (20 34 Hz) represent proportionately longer (shorter) dHD. JHD determined in solution correlates well with dHH in the solid state, and both Morris and Heinekey developed empirical relationships: dHH = 1.42 0.0167(JHD) dHH = 1.44 0.0168(JHD) (Morris) (Heinekey)

Metal-Dihydrogen (H2) Complexes (continued)

p. 93

Dynamics in MH2 and MH Complexes

Metal-Dihydrogen (H2) Complexes dynamics (cont)

p. 94

Hydrogenase Metalloenzymes

p. 95

Redox enzymes: billions of years old found in microorganisms Catalyze complete reversible interconversion of H2 & H+ / e H2 as energy source or dispose of excess electrons via H2 release High turnover rates: 104 turnovers/s H2 2 H+ + 2e

True equilibrium; position (e)affected by H2 pressure H2 + D2O HD + HDO (rx observed) pH dependent > infer that H2 is split heterolytically at metal(s)

Hydrogenase (continued)
Understanding the mechanism of hydrogenase might help scientists design clean biological energy sources, such as algae, that produce hydrogen

p. 96

p. 97

Fe Fe Hydrogenase

Molecular wire

Hydrogenase (continued)
Active-site attached only at one point

p. 98

Iron-Iron bond: Site of H2 heterolysis

CO and CN ligands On low-spin Fe(II)

Possible Mechanism for Hydrogenase: H2

2H+ +

p. 99 2e

Proposed H2ase Mechanism With dithiolate bridge Based on DFT Calculations

Overall charges not shown

p. 100

Proposed H2ase Mechanism aza-dithiolate bridge DFT calculations

Overall charges not shown

p. 101

p. 102

Hydride transfers to M, resulting olen may or may not stay coordinated Requirements (i) Vacant site. (ii) complex usually has less than 18e, Otherwise a 20 electron complex results immediately

Beta-hydride Elimination
Mechanism > Four-center transition state inferred

H M

CH2 CH2

H M C H H C

H H

H M C H2 CH2

Olen-insertion microscopic reverse reaction

critical step in olen polymerization -hydride elimination is a termination step in olen polymerization

Known structures (X-ray and/or Neutron diffraction),

Supporting the proposed four-center transition state

Stable M-alkyls No beta-hydride elimination

CMe3 CMe2Ph SiMe3

M
neopentyl

M
neophyl CMe3

M
"silyl-neopentyl"

M
norbornyl

M
benzyl

M
alkynyl

Rh(III) d 6 low-spin

Ex: Stabilize M-alkyl-to -hydride elimination: have a stable complex where ligands do not come off to create vacant site, that which is needed

-hydride elimination
Alpha-hydride elimination is the transfer of a hydride (hydrogen atom) from the alpha-position on a ligand to the metal center. The process can be thought of as a type of oxidative addition reaction as the metal center is oxidized by two electrons (Eq 1). As the reaction involves a formal oxidation of the metal, alpha-elimination can not occur in a d0 or d1 metal complex. In these cases, a variant called alphaabstraction can occur. Alpha-abstraction does not result in a change of oxidation state and the alpha-hydrogen is transferred directly to an adjacent ligand instead of the metal center (Eq 2):

Delta and gamma eliminations also exist

INSERTION REACTIONS

U = an unsaturated ligand
Insertion Reaction Net Result: Decrease in coordination, formation of new UX bond Reverse reaction referred to as deinsertion When deinsertion group is an olen > -hydride elimination

Anionic and neutral couple too form a new anionic ligand

Migratory Insertions

{makes the neutral ligand (e.g., CO) more electrophilic and Susceptible to nucleophilic attack by the anionic ligand.}

Mechanistic Considerations: CO Insertion or Me Migration

Mechanistic Considerations: CO Insertion or Me Migration

For a generic insertion of CO into a metal alkyl bond, one can envision two mechanistic extremes, one in which the methyl migrates to the carbonyl and a second in which the carbonyl moves and inserts into the metal-methyl bond. Either way, this generates an open coordination site denoted here as the small box:

Label on one CO (13CO) cis to an acyl group, can differentiate the two possible mechanisms. If the CO moves during the deinsertion, then it can only move to a cis position, displacing another CO in the process. As there are four cis CO's and only one of them is labeled with 13CO, then we would expect to remove the labeled carbonyl 25% of the time. If the methyl group moves, it can also displace the 13CO 25% of the time. However, if it moves into one of the other three cis positions, it can do so in a cis and trans fashion with respect to the 13CO, something that can be detected spectroscopically:

This subtle but important difference was studied by Calderazzo (see Ang. Chem. Int. Ed. Eng. 1977, 16, 299 for his classic IR spectroscopy study) who examined the reverse reaction, deinsertion of CO from a metal acyl complex. By the Principle of Microscopic Reversibility, the insertion and deinsertion must follow the same mechanistic route, only in different directions.
CO 25% OC OC CO CH3

Mn
CO CO

CO OC OC

CO CH3

CO

Mn
CO

CO

CO

OC OC

Mn
CO

O CH3

CO 50%

CO CH3

OC OC

Mn
CO

CO 25% OC OC

CO CH3

Mn
CO

Most systems undergo migration; both mechanisms can occur

82 % yield 95 % e.e. Inversion on Fe Et migrated

Optically active compound. CH3NO2, MeCN, Me-migration DMSO, DMF, proplyene carbonate, HMPA CO migration
Possible intervention of 2-acyl-intermediate could make the interpretation of which is the migrating group less than denitive RBJordanp. 170
P

Retention on Fe CO migrated

Fe
C

O
CH3

Electron-transfer Induced Insertion Reaction Chemistry

CpFe(CO)(PPh3)Me CO few % Cp2Fe+ O (Ph3P)(CO)CpFe C Me complete in <2 min under similar conditions rate enhancement ~ 107!!

1 atm CO
0 C, CH2Cl2

N.R. after 5 days (rate < 10-7s-1)

Ferrocinium cation

Mechanism:
CpFe(CO)(PPh3)Me

[CpFe(CO)(PPh3)Me]+ CO

O (Ph3P)(CO)CpFe C Me 18 e 17 e (Ph3P)(CO)CpFe

O C Me

(oxidizes starting material)

Alkene (Olen) Migratory Insertions

This is the basis for almost all transition metal-based polymerization catalysts. A polymerization rxn is just many, many migratory insertions of an alkene and alkyl (the growing polymer chain) interspaced with alkene ligand addition reactions.

Alkynes can also do migratory insertions to produce vinyl groups:

Oxidative Addition Reactions

Oxidative addition is formally the microscopic reverse of reductive elimination, and it is not surprising that a series of reactions

involving an oxidative addition, a rearrangement and then a reductive elimination form the basis for a variety of industrially important catalytic cycles
Oxidative addition reactions are most facile when there is a good twoelectron redox couple. In other words, both the starting and nal oxidation states are relatively stable. For example, oxidative addition from Ir(I) to Ir(III) is common but an oxidative addition from Fe(III) to Fe(V), while possible, is generally unlikely The more reduced a metal center is (also electron-rich because of ligands), the greater the reactivity towards oxidative addition. The likelihood of oxidative addition of AB to a metal, M, depends on the relative strengths of the AB, MA and MB bonds. For example, oxidative addition of an alkane is much less common than oxidative addition of an alkyl halide. For the alkane case, the C-H bond is fairly strong compared to the M-H and M-R (R = alkyl) bonds

Vaska Complex Oxidative Addition Reactions

Reductive Elimination Reactions

Eliminating groups must be

cis

But important; CH activation

If we consider that the DH-H = 104 kcal/mol and that the DM-H is 50-60 kcal/mol we see that these are essentially balanced and there should be no thermodynamic preference for a dihydride versus a reduced metal center. But DR-H is typically 100 kcal/mol versus a metal alkyl bond strength of 30 to 40 kcal/mol. We see that the thermodynamic situation is again approximately balanced with a slight preference for the forward reaction. DR-R is typically around 90 kcal/mol, so for two alkyl substituents, there is a strong thermodynamic driving force for the reaction to go to the right. C-C bond activation is unusually rare, but more examples continue to be found.

Transition Metal Carbene Complexes

Carbenes: neutral divalent six-electron carbon atom species

Ground-state, single or triplet, depends on R and R

Transition Metal Carbene Complexes 2

M-carbon double bonds > Metal-carbene complexes 2 types

Fischer carbene complexes (right) low oxidation state M; heteroatoms at carbene carbon atom E.O. Fischer (1st Carbene complex (1964, then Nobel Prize with Wilkinson, for metallocenes) Schrock carbene complexes: higher oxidation state; C or H substituents at carbene C-atom
alkylidene complex Richard Schrock MIT, 2005 Nobel Prize for olen metathesis (shared with Robert Grubbs (Cal Tech) and Y. Chauvin (France).

Transition Metal Carbene Complexes 3

MO/AO perspective: one lone pair is donated from the singlet carbene to an empty d-orbital on the metal (red), and a lone pair is back-donated from a lled metal orbital into a vacant pz orbital on carbon (blue). There is competition for this vacant orbital by the lone pair(s) on the heteroatom, consistent with our second resonance structure. Overall, bonding resembles that of carbon monoxide. Therefore, carbene ligands are usually thought of as neutral species, unlike dianionic Schrock alkylidenes (which usually lack electrons for back-donation). However, electron counting is just a formalism!

Transition Metal Carbene Complexes 4 Nucleophilic attack on coordinated carbonyl, then alkylation

Protonation (akylation) of neutral acyl-complex

Transition Metal Carbene Complexes 5

Addition of ROH to a coordinated isocyanide ligand

Synthesis of a N-heterocyclic Carbene Complex. NHCs are useful coligands (ancillary ligands) in reactive transition-metal carbene complexes.

Transition Metal Carbene Complexes 6

The rst non-stabilized (i.e., with C-heteroatom) metal carbene complex).

Schrock Carbene Complexes: -deprotonation of a metal alkyl

Transition Metal Carbene/Carbyne Complexes 7

Metal-alkyl hydride abstraction:

Metal Carbyne Complexes Metal-carbon triple bond

Made serendipitously

Transition Metal Carbyne Complexes 8

Reactions of Fischer Carbenes

Heteratom substitution reects electrophilic nature of the C-atom

Methyl group CH acidity is enhanced because the carbanion formed is stabilized by the carbene group:

M-carbenes generally not good carbene transfer agents, however:

A free carbene is not likely formed

Reactions of Fischer Carbenes: continued

Olen Metathesis or Cyclopropanation Olen [2 + 2] addition to Mcarbene gives a metallocyclobutane. Then, a retro [2 + 2] could give olen metathesis. However, cyclopropane formation is more (energetically) likely:

Reaction stereospecic

First isolated metallocyclobutane complex Grubbs, 1980

Reactions of Fischer or Schrock Carbenes

Another example: if you replace CO by PPh3 > proceeds with enantiomeric excess

Schrock carbenes are more reactive than Fischer carbenes The alkylidene carbon is nucleophilic

Reactions of Schrock Carbenes

Reactions of Schrock Carbenes - continued

Tebbe chemistry Tebbe reagent

Reactions of Schrock Carbenes - continued

Carbene Migratory Insertions:

If we electron-count the carbene as a dianionic ligand we are reacting a monoanionic ligand (X) with a dianionic ligand (carbene) to make a new monoanionic ligand. Now formally a reductive coupling reaction (since the metal is being reduced and we are coupling together two ligands). One Can/Should consider the carbene (or alkylidene) as a neutral ligand. For X = H, the reverse reaction is called an -hydride abstraction or elimination.

Carbene Migratory Insertion:

Note: This is Schrock type M-carbene complex, where carbene carbon is not electrophilic (like CO is traditional migration reactions). The reaction is probably aided by the overall metal complex positive charge.

Alkene/Olen Metathesis Reaction Types

Very useful in natural product syntheses

Very useful in polymer syntheses

Olen Metathesis Catalysts (there are many others)

From, Organometallic chemistry and catalysis, Didier Astruc (Springer, 2007)

From, Organometallic chemistry and catalysis, Didier Astruc (Springer, 2007)

Chauvin Mechanism of Alkene Metathesis

D2C=CD2 is the product from the deuterated substrate, only. From 1:1 substrate mixture, of you get 1:2:1 mixture of ehtylenes

ROMP Examples
Schrock asymmetric catalyst (based on BINOL)

First ROMP commercial catalyst

ROMP & RCM

ROMP incredibly useful/practical in materials/polymer syntheses Ring closing metathesis (RCM) incredibly useful in natural product and pharmaceutical syntheses.
Hepatitis B protease inhibitor

Cp*2TaV

H CH2 H2O Cp*2TaIII CH3

H2O

H2O

SiH4 Oxidative Addition H Cp*2TaV Alpha Elimination H O CH3 SiH3

CH4 + H2 + Cp*2TaV OH CH2 Cp*2TaIII O

Cp*2

TaV

Migratory Insertion may be disfavored (equilibrium lies to to the left) due to higher energy of the insertion product (right side). BUT - this higher energy may favor reactivity with the insertion product

Pairwise Mechanism:
R R' R R'

'

M R M R' R M R'

R'

Carbene "stepwise" mechanism:

M CH2 M + R R H2C R CH R + R' R' M R R' R R' R' R' M +

Distinguished by an experiment with 1:1 mixture of: Metathesis products: from 100% protio + substrate These olefins do not back-react with catylst (i.e. are not metathezised) due to A: low concentration of ethylene in reaction mixture B: stabilization of phenanthene

D2 D2

By Pairwise Mechanism (after initiation)

M

D D
or

M D D

+ H2C

CH2

Predicts 1:1 product distribution

+ D2C

CD2

CH2

H2C M
+

CH2

M
+

CH2

Stepwise

CH2 CD2

H2C M
+

CD2

D2C M M
+

CD2

CD2
+

This leads to the observed product distribution: 1:2:1 H2C=CH2 : H2C=CD2 : D2C=CD2

EXAMPLES:

Homogeneous Catalysis

Wacker Process oxidation C2H4 (ethylene) + O2 > CH3C(O)H (acetaldehyde) (Pd, Cu) Monsanto acetic acid synthesis CH3OH (methanol) + CO > CH3C(O)OH (acetic acid) (Rh catalyst) Alkene Hydrogenation CH3CH2=CH2 + H2 > CH3CH2CH3 (all gases) Gf = 20.6 kcal/mol Hydroformylation Polymerization Ziegler-Natta (1963 Nobel Prize) Olen metathesis n CH2=CHR > [CH2-CHR]n

(Chauvin, Schrock, Grubbs, 2005 Nobel Prize)

Water gas-shift reaction H2O + CO > H2 + CO2 (all gases) Gf = 6.9 kcal/mol Fischer-Tropsch reaction Coupling reactions

Catalyst: Increases overall rate of a reaction Does not change equilibrium position Signicantly lowers activation energy Is not used up in the reaction Normally interacts with substrate > alternative reaction pathway

Homogeneous Catalysis

A Catalyst Signicantly Lowers the Reaction Activation Energy

Products of un-catalyzed and catalyzed reactions may be different

 Rate of all of the steps of the reaction are the same for catalytic cycle But, of course, the slowest individual step (weakest link) dictates the Rx rate i.e., turnover limiting step TON, turnover #; # of reactant molecules the catalyst converts to product TOF, turnover frequency; TON per unit time To achieve high TON, reactants and products cannot bind too tightly to M A catalyst may inuence initial product distribution, giving preferential formation of a less thermodynamically stable product, i.e., selectivity

Kinetic Competence
Catalysis is a kinetic phenomenon: Activity may rely on minor (even minuscule) component (of catalyst or intermediate) Danger in relying too much on spectroscopic studies of catalytic systems where you see only major components Must demonstrate a given step is kinetically competent to carry out the reaction. proposed intermediates reacts sufciently fast to account for product formation One issue is (has been) catalyst decomposition to metal, M(0) --- > heterogeneous catalysis homogeneous catalyst is heterogeneous catalyst in disguise (Crabtree) Examples; hydrogenation catalysts are Pt group metal (Ru, Os, Rh, Ir, Pd, Pt) halides. MX2 in polar solvent with H2 (g) --- > colloidal metal particles (heterog.) Test: Add Hg(l), which selectively poisons any heterog. Pt group M Absorption to active sites

The Monsanto acetic acid process is the major commercial production method for acetic acid. Methanol, which can be generated from synthesis gas ("syn gas", a CO/H2 mixture), is reacted with carbon monoxide/catalyst > acetic acid. In essence, you have the insertion of carbon monoxide into the C-O bond of methanol, i.e. the carbonylation of methanol. This process operates at a pressure of 3060 atm and a temperature of 150200 C and gives a selectivity greater than 99%. Limitations/Drawbacks 1. Rhodium is an expensive starting material. 1 mole of RhCl33H2O costs ~ $30,000! 2. I2 is cheap (about $20 per mole), but is extremely corrosive. Other halogens or halogen substitutes do not work nearly as well. The Monsanto process has largely been supplanted by the Cativa process, a similar iridium-based process developed by BP Chemicals Ltd which is more economical and environmentally friendly

The Cativa process: A method for the production of acetic acid by carbonylation of MeOH. The technology, similar to the Monsanto process, was developed by BP Chemicals and is under license by BP Plc.[1] [2]The process is based on an iridium-containing catalyst, such as the complex [Ir(CO)2I2]. The Cativa and Monsanto processes are similar; they can use the same chemical plant. Initial studies by Monsanto had shown that iridium to be less active than the rhodium for the carbonylation of methanol. Subsequent research, however, showed that the iridium catalyst could be promoted by ruthenium, and this combination leads to a catalyst that is superior to the rhodium-based systems. The switch from rhodium to iridium also allows the use of less water in the reaction mixture. This change reduces the number of drying columns necessary, decreases byproducts formation, and suppresses the water gas shift reaction. Furthermore, the process allows a higher catalyst loading. Compared with the Monsanto process, the Cativa process generates less propionic acid by-product.

Homogeneous Hydrogenation Catalysis Wilkinsons Catalyst (1966)

Nobel Laureate (1973; on another subject)

Catalyst Synthesis: RhCl3(H2O)3 + 4 PPh3 >

Formally: double bond attacks H+

RhCl(PPh3)3 + O=PPh3 + 2 HCl + 2 H2O

Chiral Molecules Enantiomers with different Biological Effects

(R)-Limonene smells of oranges (S)-limonene smells of lemons.

Insects use chiral chemical messengers (pheromones) as sex attractants; one of the enantiomers of the insect pheromone, olean, attracts male fruit ies, while its mirror image operates on the female of the species. Most drugs consist of chiral molecules. Since a drug must match the receptor in the cell, it is often only one of the enantiomers that is of interest (active). In the 1960s, the drug thalidomide was prescribed to alleviate morning sickness in pregnant woman. Tragically, the drug also caused deformities in the limbs of children born by these woman. May have been the wrong enantiomer (?). In drug development, pharmaceutical companies are required to carefully purify and test both enantiomers.

Catalytic Asymmetric Syntheses

Early success, 1968: Dr William S. Knowles, Monsanto Company, St Louis, USA Following (i) Wilkinson catalyst discovery, and (ii) synthetic methods for chiral phosphines, Knowles strategy: replace triphenylphosphine in Wilkinsons catalyst with the enantiomer of a known chiral phosphine and hydrogenate a prochiral olen.

Knowless catalytic asymmetric hydrogenation of -phenylacrylic acid using a rhodium catalyst containing (-)-methylpropylphenylphosphine (69% ee) gave (+)-hydratropic acid in 15% ee.

Industrial synthesis of the rare amino acid L-DOPA

Proved useful in the treatment of Parkinsons disease
Early BIG Success in Catalytic Asymmetric Syntheses Knowles (Monsanto)

enamide

protected AA

Monsanto Process - rst commercialized catalytic asymmetric synthesis employing a chiral transition metal complex. In operation since 1974.

Mechanism (J. Halpern): Asymmetric Hydrogenation of Enamides

COD or
other

weak ligand(s) dissociated

rate limiting

Stepwise addition of H

Rh(III)-alkyl complex

Noyoris (R. Noyori, Nagoya U.) General Hydrogenation Catalysts

1. Developed Widely Useful BINAP Chelating Diphosphine

Noyoris (R. Noyori, Nagoya U.) General Hydrogenation Catalysts

2. Application

Noyoris catalyst

Noyoris (R. Noyori, Nagoya U.) General Hydrogenation Catalysts 3. Application Expand synthetic organic utility:
With Ru, hydrogenation of carbonyl group (rather than olen)

The (R)-BINAP-Ru-(II)-catalyzed hydrogenation of acetol to (R)-1,2 Propanediol: Used for the industrial synthesis of antibacterial levooxacin.

2001 Nobel Prize in Chemistry

Catalytic asymmetric synthesis Dr William S. Knowles, Monsanto Company, St Louis, USA; Professor Ryoji Noyori, Nagoya University, Nagoya, Japan: Professor K. Barry Sharpless, The Scripps Research Institute, La Jolla, CA USA. Nobel Prize their development of catalytic asymmetric synthesis. Knowles and Noyori receive half the Prize for: their work on chirally catalysed hydrogenation reactions and Sharpless, the other half of the Prize for: his work on chirally catalyzed oxidation reactions.

Key: enantiopure dialkyltartrate ligands for Ti Also, developed Osmium catalyzed asymmetric dihyroxylation of olens. Chemistry Nobel Prizes: Four (4) in Organometallic Chemistry: Ziegler-Natta, Wilkinson, 2001/Enantioselective organic rxs., 2005/ Olen Metathesis

Water gas-shift reaction H2O + CO <> H2 + CO2

kcal/mol

(all gases) Gf = 6.9

Thermal or Photochemical Water-Gas Shift Reaction

The water-gas shift reaction (WGS) is widely employed in industry to enrich the hydrogen content in water gas (synthesis gas; Syngas; H2(g)/CO(g) ) after the steam reforming of methane. The WGS reaction is typically performed at high temperatures over heterogeneous iron oxide or copper oxide catalysts. Interest in the WGS shift reaction under mild, homogeneous conditions has been long-standing. Many soluble transition metal carbonyl complexes show activity for thermal WGS catalysis, usually in basic media. WGS activity is promoted photocatalytically, where the photons are typically used to open coordination sites by the expulsion of CO or photoextrusion of H2 from the transition metal center.

Proposed mechanism for the thermal (or hv) WGS reaction catalyzed by homoleptic Group 6 carbonyls. Chem. Rev. 2007, 107, 4022. A. J. Esswein & D. G. Nocera

hv

1 photon

Photochemical Water-Gas Shift Reaction

bipy; 2,2-bipyridine