Or

Fischer and Schrock Carbenes:

A Brief Overview
Organic Pedagogical Electronic
Network Alison Brown & Nathan Buehler
University of Utah
Free Carbenes: A Brief Primer
A carbene is any neutral carbon species which contains a
non-bonding valance pair of electrons

- The simplest example of a carbene is methylene

- Traditional organic chemistry requires photolysis or H
thermolysis for carbene formation (specifically methylene) C
- Carbenes exist in either the singlet or triplet state H
Methylene
Both singlet and triplet carbenes are highly reactive,
reacting with all C—H and C=C bonds
H
C
Singlet state carbenes have spin-paired electrons, and can be thought of H
as having Zwitter-ionic character
As a result, the singlet state is highly reactive
Singlet

H
Triplet state carbenes are considered to be in the ground state, yet still C
highly reactive H
Chemical behavior similar to radical chemistry Triplet
Wiki Page: http://en.wikipedia.org/wiki/Carbene
Other Helpful References: http://chemistry.caltech.edu/courses/ch242/L20.pdf,
Historical Metal-Carbene Complexes
Early Examples Overview:
The first transition metal stabilized carbene
was developed by Fischer in 1964

O OMe
O Me 3O BF 4
W(CO)6 + MeLi Li (CO)5W (CO) 5W (CO)5W

(Fischer, E. O.. Angew. Chem.

Int. Ed. Engl. 1964, 3, 580.)

Mechanistic Implications:
The next major variety of carbene was
The Fischer carbenes are electrophillic
developed by Schrock in 1974
due to the formally empty pi orbital
Cp Cl
Cp Base Cp
Ta(CH3)3
Cp TaCl(CH3) 2 Ta CH 2
Cp Cp In contrast, Schrock carbenes are
Me

(Schrock, R. R. J. Am. Chem.

nucleophillic in nature, and behave as
Soc. 1974, 96, 6796.) strong bases.

To explain the differences in reactivity one should consider FMO theory, transition metal character, and available back-bonding.
Schrock carbenes have a empty metal-like LUMO and a filled ligand-like HOMO, while in comparison the Fischer carbenes have
filled metal based HOMO and a ligand based LUMO. As a result Schrock carbenes experience little backbonding and exhibit
significant ionic character due to the early transition metal character. Fischer carbenes have a low lying metal orbital and a high
lying empty ligand orbital, and this arrangement allows for particularly strong backbonding.

Wiki Page: http://en.wikipedia.org/wiki/Transition_metal_carbene_complex

Other References: Schrock Paper, Fischer
Modern Metal-Carbene Complexes
Overview
Very recent work has focused on the use of Au as a catalyst capable of performing
enantio-selective reactions with carbene intermediates.
Other interesting work by de Bruin involves radical Co chemistry to generate a
carbene intermediate

Examples
OMe
cat.
OH R1 O O
R3 [(C 2H 4)PtCl 2]2 R1
R3 R3
R1 THF, rt
R2 R2 [Pt] R2

O
N
R2
OMe
cat.
YH Y R1
R2 [Pt] X or
X R2
X-Y = NR 3-O,
R1 [Pt] N
R1 O-NR3 O
R2

R1

Wiki Page: http://en.wikipedia.org/wiki/Transition_metal_carbene_complex

Other References, Chem. Sci., 2013, 4, 1053-1058., Acc. Chem. Res., ASAP., Chem. Eur. J., 2013, 19, 12953-12958., J. Phys.
Chem. A, 2013, 117,9266-9273.,
Modern Metal-Carbene Complexes
Example Mechanism

Wiki Page: http://en.wikipedia.org/wiki/Transition_metal_carbene_complex

Other References, Chem. Sci., 2013, 4, 1053-1058., Acc. Chem. Res., ASAP., Chem. Eur. J., 2013, 19, 12953-12958., J. Phys.
Chem. A, 2013, 117,9266-9273.,
Modern Metal-Carbene Complexes
Future Directions
Be BeCH 2 CH 2

Generation of the ‘simplest carbene’,

BeCH2. 2p x

Computational studies indicate that

2p y
formation of BeCH2 is thermodynamically
favorable but that mechanistic or kinetic
2pz
reasons prevent BeCH2 from being made 1b1
or persisting.

2s

3a1

Wiki Page: http://en.wikipedia.org/wiki/Transition_metal_carbene_complex

Other References, Chem. Sci., 2013, 4, 1053-1058., Acc. Chem. Res., ASAP., Chem. Eur. J., 2013, 19, 12953-12958., J. Phys.
Chem. A, 2013, 117,9266-9273.,
Problems
N
O O (5 mol%)
Cl Au O S
S
Cl

ClCH 2CH 2Cl, rt, 3h

O

N2 Catalyst (2 mol%) O O
OEt CO (10 bar)
H + PhNH 2 HN OEt
O Solvent, 50 oC Ph
OAc
(R)-xylxy-BINAP(AuCl) 2 (2.5 mol %) Ac
AgSbF6 (5 mol %)

MeNO 2, -25 oC
(NHC)AuCl cat. =

CF 3

Ph (NHC)AuCl cat. (5 mol %)

O Ph AuCl
OH AgOTf (10 mol %), CDCl3
OPiv N
H N NH
HN N H
N
ClAu
OPiv
F 3C

O
S IPrAuNTf 2 (5 mol %)
OH H
(ClCH 2) 2 rt, 3h O O
Cl
S
Cl

References
Acc. Chem. Res., ASAP., Acc. Chem. Res.,ASAP.,
Contributed by:
Alison Brown & Nathan Buehler (Undergraduates)

University of Utah, 2013

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