Carbenes

.
: C . C
- Stable Free Carbenes :
Singlet Triplet
CMe3

F3C
CMe3
CF3 N
Triplet
:C :C :C .C.
N Tomioka, JACS,
P NiPr2 NiPr2 2003, 14664

iPr2N

Science, 2000, JACS, 2004, 8670

288, 834

Arduengo Carbene or CMe3

Guy Bertrand
NHC (N-Heterocyclic Carbene)
 Transition Metal Carbene Complexes
FISCHER SCHROCK
- Electrophilic Carbon - Nucleophilic Carbon

:
R R
: :
R R

neutral CR2 (L-type ligand) CR22- (X2-type ligand)

(similarities to PR3) (similarities to M=O or M=NR)
properties strong -donor strong -donor
poor or OK -acceptor strong -donor
2-electron donor 4-electron donor

R = -donor
typical R groups in CR2 (OR, NR2, Ph) R = H, Alkyl

Late TMs, Low oxidation Early TMs (often d0), High

typical metals
states (Mo0, Fe0 etc.) oxidation states (TaV, WVI)
-acceptors Cl-, Cp-, Alkyl,
typical co-ligands
(CO, CNR, P(OR)3) Imido, Amido
 Transition Metal Carbene Complexes
▪ Carbenes (CR2) – these are not redox active ligands – i.e. Fischer or Schrock
complexes have the same number of electrons. The difference is whether the
carbene carbon is nucleophilic (Schrock) or electrophilic (Fischer).

Fischer Carbene Schrock Carbene

. .
R - neutral triplet carbene
M . . C - 2 covalent bonds Ligands viewed as
X R - 2 electron donor being neutral 2e- donors

M : C
R

- only one way to look at

: - dianionic CR22-
a Fischer carbene R - 2 bonds
M :C Ligands not neutral
- neutral singlet carbene R ( and  donation)
- 1 donor covalent bond + - 4 electron donor
weak -backdonation
- 2 electron donor
 Transition Metal Carbene Complexes
CO FISCHER

N N
OC CO Ar Ar
Cr O C CH3
OC Me Ta
Cl
- Examples : Ph Ru CHPh
CH2
CO
Cl
PCy3

O Me
SCHROCK
M C
Ph

- Exceptions :

If Schock If Fischer TaV = d0

WVI = d0 WIV = d2 2 x Cp- = 12
2 x Cp- = 12 2 x Cp- = 12 CH3 CH3
W Ta Me- = 2
Me- = 2 Me- = 2 CH2 CH2 CH22- = 4
CH22- = 4 neutral CH2 = 2 Total = 18
Total = 18 Total = 18

FISCHER !!! SCHROCK

Synthesis of Carbene Complexes
Acyl or Iminoacyl Complex + Electrophile :

O O
Me- Me I
M CO M C M C

[Pt(C NMe)4]2+ + 4 MeNH2 [Pt{C(NHMe)2}4]2+

From alkyls with -hydrogens

Base M C R
R
H - H+
M R
R - H-
Lewis acid M C R
(e.g. BAr3 or CPh3+) R

Using a carbene source (e.g. a diazoalkane, R2C=N=N)

LxM + CH2N2 LxM=CH2 + N2

 Metal Carbyne Complexes
- Also Fischer and Schrock bonding extremes, but the distinction is less
marked → considerable ambiguity in many cases.

FISCHER SCHROCK
Br2
Br(OC)4W CR (dme)Br3W CR
dme
d4 dme = 1,2-dimethoxyethane d0
:

:
: R : R

:
CR- = an LX-type ligand CR3- = an X3-type ligand
(similarities with N3- and C4-)

1 x -donor 1 x -donor
1 x -donor 2 x -donor
1 x -acceptor
 Metal Carbyne Complexes
Fischer Carbyne Schrock Carbyne
▪ Carbynes (CR) are not redox active ligands
M : C R

Ligand cationic
- cationic CR+ (2 e- donor)
- 1 donor covalent bond +
2 vacant p-orbitals for M-->L
-backdonation

. .
M : C R . C R Ligands viewed as
M .
being neutral 3e- donors

- neutral doublet CR (3 e- donor) - neutral quartet CR (3 e- donor) - useful for electron counting
- 2 covalent bonds + - 3 covalent bonds if you don't know if a CR2
1 vacant p-orbital for M-->L ligand is a Fischer or
-backdonation Schrock carbene.

:
:

Ligands anionic
M : C R M : : C R
- Better method for working
out the formal oxidation
- anionic CR- (4 e- donor) - trianionic CR3- (6 e- donor) state of a metal coordinated
- 2 donor covalent bonds + - 3 donor covalent bonds to a CR2 ligand. Using this method,
1 vacant p-orbital for Schrock carbynes are almost
M-->L -backdonation always found with d0-metals
Metal Carbide Complexes

C. C. Cummins et al.,
Chem. Commun., 1997, 1995