Metal carbonyls may be mononuclear or polynuclear

Characterization of metal carbonyls

IR spectroscopy M-C-O (C-O bond stretching modes)

 Effect of charge

(free CO) 2143 cm-1

Lower frequency, weaker CO bond

Effect of other ligands

Increasing elec
donating ability of
phosphines
PF3 weakest donor (strongest acceptor)
PMe3 strongest donor (weaker acceptor)
The number of active bands
as determined by group theory
 Typical reactions of metal carbonyls

Ligand substitution:
Cr(CO)6 + CH3CN Cr(CO)5(CH3CN) + CO

Always dissociative for 18-e complexes, may be associative for <18-e complexes

Migratory insertion:

CH3 H3 C H3 C CO
OC CO C CO CO C CO
Mn O Mn O Mn
OC CO OC CO OC CO
CO CO CO
 Metal complexes of phosphines
PR3 as a ligand
Generally strong  donors, may be π-acceptor
M-PR3 strong trans effect
Electronic and steric properties may be controlled
Huge number of phosphines available
 Metal complexes of phosphines

M-PR3

Basicity: PCy3 > PEt3 > PMe3 > PPh3 > P(OMe)3 > P(OPh)3 > PCl3 > PF3
Can be measured by IR using trans­M(CO)(PR3) complexes

Steric properties: 

 R1 R2P
M
M P PR2
R2

R3

The cone angle
Rigid structures create chiral complexes
apex angle of a cone that encompasses
the van der Waals radii of the outermost
atoms of the ligand
 Typical reactions of metal-phosphine complexes

Ligand substitution:

HCo(CO)4 + PBu3 HCo(CO)3(PBu3) + CO

HRh(CO)(PPh3)3 + C 2H4 HRh(CO)(PPh3)2(C2H4) + PPh 3

presence of bulky ligands (large cone angles)
can lead to more rapid ligand dissociation 

Very important in catalysis

Mechanism depends on electron count
Metal hydride and metal-dihydrogen complexes

M H Terminal hydride (X ligand)

H Bridging hydride (-H ligand, 2e-3c)

M M

H
M Coordinated dihydrogen (2-H2 ligand)
H

Hydride ligand is a strong  donor and the smallest ligand available

H2 as ligand involves -donation and π-back donation
 Synthesis of metal hydride complexes

IrCl(CO)(PPh3)2 + H 2 Ir(H) 2Cl(CO)(PPh3)2

Et3N
RuCl2(PPh3) 3 + H 2 RuHCl(PPh3) 3 + Et 3N.HCl

Co2(CO) 8 + H 2 2 HCo(CO)4

[Fe(CO) 4] 2- + H + [HFe(CO)4]-

Cp2ZrCl2 + NaBH 4 Cp2ZrHCl

Characterize these kinds of reactions.

 Characterization of metal hydride complexes

1
H NMR spectroscopy

High field chemical shifts ( 0 to -25 ppm usual, up to -70 ppm possible)
Coupling to metal nuclei (101Rh, 183W, 195Pt) J(M-H) = 35-1370 Hz
Coupling between inequivalent hydrides J(H-H) = 1-10 Hz
Coupling to 31P of phosphines J(H-P) = 10-40 Hz cis; 90-150 Hz trans

IR spectroscopy

(M-H) = 1500-2000 cm-1 (terminal); 800-1600 cm-1 bridging

(M-H)/(M-D) = √2
Weak bands, not very reliable
 Some typical reactions of metal hydride complexes

Transfer of H-
Cp2Zr(H)2 + 2CH 2O Cp2Zr(OCH 3)2

Transfer of H+

HCo(CO) 4 H+ + [Co (CO)4]- A strong acid !!

Insertion

IrH(CO)(PPh 3) 3 + (C 2H4) Ir(CH 2CH3)(CO)(PPh3)3

A key step in catalytic hydrogenation and related reactions

 Bridging metal hydrides

Anti-bonding

Non-bonding

2-e ligand 4-e ligand

bonding
 Metal dihydrogen complexes
M
Characterized by NMR (T1 measurements)

H H

Very polarized
i
P Pr3 +, -
H
CO H
M OC W
H OC H
PiPr3

back­donation to * orbitals of H2
the result is a weakening and lengthening of 
the H­H bond in comparison with free H2

If back-donation is strong, then the H-H bond is broken (oxidative addition)

 Metal-olefin complexes

2 extreme structures

sp3
sp2

Zeise’s salt
metallacyclopropane π-bonded only
Net effect weakens and lengthens 
the C­C bond in the C2H4 ligand (IR, X­ray)
 Effects of coordination on the C=C bond

Compound C-C (Å) M-C (Å)

C2H4 1.337(2)
C2(CN)4 1.34(2)
C2F4 1.31(2)
K[PtCl3(C2H4)] 1.354(2) 2.139(10)
Pt(PPh3)2(C2H4) 1.43(1) 2.11(1)
Pt(PPh3)2(C2(CN)4) 1.49(5) 2.11(3)
Pt(PPh3)2(C2Cl4) 1.62(3) 2.04(3)
Fe(CO)4(C2H4) 1.46(6)
CpRh(PMe3)(C2H4) 1.408(16) 2.093(10)

C=C bond is weakened (activated) by coordination

 Characterization of metal-olefin complexes

IR
(C=C) ~ 1500 cm-1 (w)

NMR
1
H and 13C,  < free ligand

X-rays
C=C and M-C bond lengths
indicate strength of bond
Reactions of metal-olefin complexes
Metal alkyl, carbene and carbyne complexes
 Metal-alkyl complexes
Main group metal-alkyls known since old times
(Et2Zn, Frankland 1857; R-Mg-X, Grignard, 1903))

Transition-metal alkyls mainly from the 1960’s onward

W(CH3)6 Ti(CH3)6 PtH(CCH)L2

Cp(CO)2Fe(CH2CH3)6 [Cr(H2O)5(CH2CH3)6]2+

Why were they so elusive?

Kinetically unstable (although thermodynamically stable)

 Reactions of transition-metal alkyls

R
LnM LnM + R-X
X

LnM R + H+ LnM+ + R-H

Blocking kinetically favorable pathways allows isolation of stable alkyls 
 Metal-carbene complexes
pz pz

sp2 sp2 .
: C
R . C
R

R R

singlet carbene triplet carbene

.
d d
: .
.
d d
M : C
R
M . C
R

R R

L ligand X2 ligand
Late metals Fischer carbene Schrock carbene Early metals
Low oxidation states High oxidation states
Electrophilic OR Nucleophilic
M C
R
R
M C
R
+
­ OR
M C
R
Fischer-carbenes
 Schrock-carbenes

Synthesis

Typical reactions

O
X H
t-Bu
Np3Ta O +
Np3Ta +
X Y Y t-Bu

Compare to Wittig

+ olefin metathesis (we will speak more about that)
 Grubbs carbenes

Excellent catalysts for olefin metathesis
 Metal cyclopentadienyl complexes

Metallocenes
M
(“sandwich compounds”)

M Bent metallocenes

“2- or 3-legged
M M
piano stools” L
L L L
L
 Homogeneous catalysis:
an important application of organometallic compounds

M H
M CO
Catalysis in a homogeneous liquid phase
M H
Very important fundamentally M PR3
M Cp
Many synthetic and industrial applications
M
Fundamental reaction of organo-transition metal complexes

Reaction (FOS) (CN) (NVE)

Association-Dissociation of Lewis acids 0 ±1 0

Association-Dissociation of Lewis bases 0 ±1 ±2

Oxidative addition-Reductive elimination ±2 ±2 ±2

Insertion-deinsertion 0 0 0
 Combining elementary reactions

H H

MLn + H2 MLn (oxidative addition)

H H H H
-L
+ (ligand exchange)
MLn MLx

H H
H C C H
(insertion)
MLx
MLn
 Completing catalytic cycles
Olefin hydrogenation

H H
H C C H
(insertion)
MLx
MLn

H C C H
H H
MLn MLn + C C (reductive elimination)
 Completing catalytic cycles
Olefin isomerization
H H
H C C H
-H elimination
MLx
MLn no net reaction

H H
H H
MLx H3 C H CH3 MLx
H3 C
H C C
H
MLn
CH3
CH3

-H elimination resulting in C=C bond migration

 Completing catalytic cycles
Olefin isomerization

H H

MLx

H2
H H H H

MLx MLx
H3 C
MLx

CH3
CH3
H3 C H CH3
H C C
H
MLn
 Completing catalytic cycles
Olefin hydrogenation

H H H2 C CH2
H2
MLx

H H

MLx MLx

H H
H3 C CH3 H
H C C H
H
MLn
 Wilkinson’s hydrogenation catalyst

RhCl(PPh3)3

Very active at 25ºC and 1 atm H2

AcO
Very selective for C=C bonds
in presence of other unsaturations H2 RhCl(Ph3)3

Widely used in organic synthesis

AcO
H
H

Prof. G. Wilkinson won the Nobel Prize in 1973

 Other hydrogenation catalysts

[Rh(H)2(PR3)2(solv)2]+ With a large variety of phosphines

including chiral ones for enantioselective hydrogenation

RuII/(chiral diphosphine)/diamine

Extremely efficient catalysts for the enantioselective hydrogenation

of C=C and C=O bonds

Profs. Noyori, Sharpless and Knowles won the Nobel Prize in 2001
 Olefin hydroformylation

R R R
cat
+ H2 + CO +
H

O O

n-isomer i-isomer

Cat: HCo(CO)4; HCo(CO)3(PnBu3)

HRh(CO)(PPh3)3; HRh(CO)(TPPTS)3

6 million Ton /year of products worldwide

Aldehydes are important intermediates towards plastifiers, detergents
 Olefin hydrogenation

H H
H C C H
(insertion)
MLx
MLn

H C C H
H H
MLn MLn + C C (reductive elimination)

What else could happen if CO is present?

O
H C C O
H C C H
C C C
CO MLn MLn +
OC MLn H H C
H
CO insertion reductive elimination
R behaves as H did
Olefin hydroformylation

H H
H2C CH2
H2
MLx

H H

MLx MLx

H2
H 3C C CHO

O H
CH3 H H
H C C H H C C H
H H
MLn MLn

CO
 Catalysts for polyolefin synthesis

Polyolefins are the most important products of organometallic catalysis

(> 60 million Tons per year)

•Polyethylene (low, medium, high, ultrahigh density) used in packaging,

containers, toys, house ware items, wire insulators, bags, pipes.

•Polypropylene (food and beverage containers, medical tubing, bumpers,

foot ware, thermal insulation, mats)
 Catalytic synthesis of polyolefin

H2 C CH2

isotactic

H2 C C CH3 syndiotactic
H

atactic

Polymerization
catalysts
Monomers Polymers
 Catalytic synthesis of polyolefin

H2 C CH2

High density polyethylene (HDPE) is linear, d  0.96

“Ziegler catalysts”: TiCl3,4 + AlR3

Vacant site
+
Ti Cl + R3 Al Ti
R Coordinated alkyl

Electrophilic metal center

Insoluble (heterogeneous) catalyst
 Catalytic synthesis of polyolefin

H2 C C CH3
H

Isotactic polypropylene is crystalline

“Natta catalysts”: TiCl3 + AlR3

Vacant site
+
Ti Cl + R3 Al Ti
R Coordinated alkyl

Electrophilic metal center

Insoluble (heterogeneous) catalyst, crystal structure determines tacticity
 Catalytic synthesis of polyolefin

H2 C C CH3
H

“Kaminsky catalysts”

Vacant site
+
+ + MAO Zr
Zr
X R
X R Coordinated alkyl

Electrophilic metal center

Soluble (homogeneous) catalyst,  structural rigidity determines tacticity
 Polymerization mechanism

M X + "R-Al" M initiation
R

R'

M + M M propagation
R R

R' -H
M H + P
+H2
M M H + P termination
+HX
M X + P
 Olefin metathesis
The Nobel Prize 2005 (Chauvin, Schrock, Grubbs)

RCH=CHR  +  R'CH=CHR' 2RCH=CHR'

N N
R H
R

Cl N CMe2Ph
Ru
Mo
Cl
Ph H3 C(F2C)2CO O-C(CF3)2 CH3
PCy3

Schrock catalyst
Grubbs catalyst
 ring­closing (RCM)
(CH2)n (CH2)n +
ring­opening (ROM)

ADMET

ROMP

n
The metathesis mechanism (Chauvin, 1971)
 Concepts and skills Unit 6 Chem 76/76.1/710G (Advanced Inorgan ic Chemistry)
Chapters 13-14. Organometallic chemistry and catalysis.
Main concepts
Ligand classification and the 18-electron rule
Oxidation states, coordination numbers
Bonding of CO, alkenes, H2, carbenes to transition
metals
Phospine ligands, electronic and steric par ameters
Genera l features of metal complexes of hydride,
phosp hine, alkyl, alkene, carbene and cyclopentadienyl
ligands.
Fund amental react ions in organometallic chemistry:
Lewis acid and Le wis base association dissociation,
oxidative ad dition/reductive elimination,
insert ion/deinsertion ( -H elimination). Attack on
coordi nated ligands. Reaction mechanisms
Elements of homogeneous catal ysis: hydrogenation,
hydroformylation, metathesis, polymerization, oxid ation
Main skills
To be ab le to identify L, X, LX, LnXm ligands and their electro n
count
To be ab le to determine the number of valence electrons for a
complex and to associate those values with stable, reactive and
unstable complexes
To qualitatively describe the bonding o f metals to:
¹ -acid ligands (CO, alkenes, H2), carbe nes
To predict reactivity of metal complexes on the basis of
fundamental reac tions covered (ligand exchange, oxidative
addition-reduc tive elimination, insert ion-deinsertion, attack on
coordi nated liigands)
To explain stability/instability of metal alkyls (kinetic vs.
thermodynamic stability)
To select appr opriate characterization methods for various types of
metal complexes
To describe some important homogeneous catalysts and some
gene ral mechanisms of the catalytic reactions studied