 Diaminocarbenes (NHCs) are strong !

-donors, have reactivities like other classical 2 e- donors:

phosphines (PR3), amines (NH3), ethers
NHCs have come to replace phosphines in many organometallic and organic reactions for several
reasons
> have mostly comparable or superior activity to phosphines
> NHCs are easy to make on a large scale
> the salts of the carbenes are stable without decomposition in air
> phosphines degrade at higher temperatures and oxidize upon exposure to air

NHCs can complex with low valent and high valent transition metals, alkaline earth metals, and
lanthanides (Yt and Sc)
>No need for excess NHC ligand in reactions
> Exceptionally stable Metal-Carbene bonds give high thermal and hydrolytic durability
>Structural Versatility
>chirality > functionalization > immobilization > water solubility > chelate effects
 In the late 19th century, Nef announced that carbon can exist in divalent state.
 Efforts for CH2 from CH3Cl or CH2I2 by elimination of HCl or I2 were made
 Hermann Staudinger (Nobel laureate, 1953): Tried to prepare CH2 and related Carbenes from
diazo compounds and ketenes
 In 1956 Philpp Skell proved the existence CCl2 as a reaction intermediate\
 No success was achieved till 1990
 Carbenes are neutral compounds featuring a divalent carbon atom with only six electrons in its
valence shell.
 Carbenes, Carbenoids and Related Species
 An important class of compounds that were also considered to be “non-existent”, or
at least transient, for many years are carbenes and the various unsaturated species
related to them.
 An understanding of the behaviour of such “building block” molecules allows us to
understand many other aspects of the chemistry of the main group elements.
 Also, from a fundamental point of view, an examination of carbenoids allows us to
explore other methods of stabilizing reactive species.

 Carbenes, and the isovalent carbenoids from groups 13, 14 and 15 are compounds that
contain di-coordinate atoms and bear a pair of electrons for a total of 6 valence electrons.

 Such compounds are also often called “ylidenes”.

 The parent molecule of the family is CH2 - methylene.

 Properties prediction

 Linear carbene centre (sp hybridized with two nonbonding degenerate orbitals (px and py)
 Bending the molecule breaks this degeneracy (sp2-type hybridization)
 Bent carbene centre (sp2 hybridized with almost unchanged py orbital (called pπ), while pure px orbital
is stabilized s character (called σ)
 The linear geometry is an extreme case; most carbenes are bent
 Spin Multiplicity and Reactivity

(Bertrand, Chem. Rev., 2000, 100, 39)

 The ground-state spin multiplicity is a fundamental feature of carbenes that dictates their reactivity.
 Singlet carbenes feature a filled and a vacant orbital, and therefore, they should possess an ambiphilic
character.
 On the other hand, triplet carbenes have two singly occupied orbitals and are generally regarded as
diradicals.
 Although in theory there could be 4 possible electron configurations (Figure 3) in practice only the first three
configurations are ever observed for ground state species.
 The vast majority of stable carbenes are of the singlet (s2) type.
 The relative stability of the singlet and triplet states (energy difference between p p and s orbitals)
 Electronic effects
 Variety of factors - a particular group will tend to favour singlet or triplet.
 Steric and electronic properties of a substituent influence the electronic structure of the compound.
 The electronic effects : Inductive effects and Mesomeric (resonance) effects.

1. Inductive effects

 The relative stability of the pp and the s orbitals is determined by

the nature of the substituents adjacent to the carbenic center.

 2nd row elements have relatively small energy and size differences
between the 2s and the 2p orbitals, CH2, NH2+ has a triplet ground
state
 Inductive effects

Figure: Pertubation orbital diagrams showing the influence of the inductive effects.

 σ-electron withdrawing substituents - stabilize the σ nonbonding orbital by increasing its s character and leave
the pπ orbital unchanged. The σ - pπ gap is thus increased and the singlet state is favored

 In contrast, σ -electron-donating substituents induce a small σ - pπ gap which favors the triplet state
 Mesomeric effects

Resonance effects are best understood in terms

of the π-acidity or basicity of the substituent adjacent
to the carbenic center.

Mesomeric effects generally favour singlet species.

• X (π-electron-donating groups: -F, -Cl, -Br, -I, -NR2, -PR2, -OR, -SR, -SR3, ...)
• Z (π -electron-withdrawing groups: -COR, -CN, CF3, -BR2, -SiR3, -PR3, …..)
• The mesomeric effects: interaction of the carbon orbitals (s, pπ or px, py) and appropriate p or π
orbitals of the two carbene substituents.
 Steric Effects

 Bulky substituents clearly kinetically stabilize all types of carbenes.

 If electronic effects are negligible, the steric effects may also dictate the ground-state spin
multiplicity.
 Steric effect broadens the bond angle therefore favours triplet state (like linear geometry favors the
triplet state).

 Dimethylcarbene: Bent singlet with carbene – bond angle = 111°

 Di(tert-butyl)carbene: Triplet with carbene - bond angle = 143°

 Diadamantylcarbene: Triplet with carbene - bond angle = 152°

 Summary: Electronic Substituent Effects
Pauling 1980 (J.C.S.,Chem. Comm., 1980, 688): Singlet carbenes can be stabilized by maintaining the
electroneutrality of carbene centre using appropriate substituents. This is known as “Push-Pull”
substitution.

1. Two π-donor σ-attractor substituents, i.e., a push,push mesomeric-pull,pull inductive substitution

pattern e.g. Diaminocarbenes.

2. Two π-attractor σ-donor substituents, i.e., a pull,pull mesomeric-push,push inductive substitution

pattern e.g. Diborylcarbenes.

3. 3. A π-donor and a π-acceptor substituent, i.e., a push,pull mesomeric substitution pattern; the
inductive effects are not of primary importance here, e.g. Phosphinosilyl carbenes.

Triplet carbenes can be stabilized kinetically by protecting the highly reactive carbene center by bulky substituents.
Singlet carbenes could be easier to stabilize by designing appropriate substituents.
 “Stable” Triplet Carbenes C

Because of their diradical nature, triplet carbenes are expected to be much more
reactive than their singlet analogues - this is the case. Triplet carbenes generally have
half-lives in the ps or ms ranges and are able to react with many compounds that are
often considered inert. In this context, triplet carbenes are considered exceptionally
“stable” if their half-lives can be measured in the millisecond range or longer.

The rapid demise of the triplet carbenes means that they are generally studied in situ
using kinetic and spectroscopic methods (e.g. Laser Flash Photolysis) in solution or
frozen matrices, or by a variety trapping reactions/product studies.

Tomioka et al. (Tomioka, Acc. Chem. Res., 1997, 30, 315) have used sterically demanding
substituents to make triplet carbenes that are incredibly long-lived.

h
C N N C + N2
 “Stable” Triplet Carbenes

When they used bulky alkyl-substituted

aryl groups such as Mesityl, Duryl or
Me5C6, the half-lives increased, but the
carbene reacted with the ortho
substituents via a radical C-H activation
process.

Thus they replaced the o-Me groups

with a halogen of comparable size:
Br. They also noticed that meta and
para substituents stabilize the
carbene even more. This is known
as a “butressing” effect.
 Attempts for Isolation of Triplet Carbenes
Zimmermann, Platz, and Tomioka work

Up to now Most Stable Indefinitely stable in crystal state at room temp and
at 130 K in solution
Room temperature half-life is 16s in solution state
Triplet Carbene Reactivity
Amino- substituents enhances the stability
• Tried to prepare the 1,3-diphenylimidazolidin-2-ylidene
• Cross-coupling experiments did not support an equilibrium between {IIa}2 and the
two carbene units, later Denk and coworkers provide some evidence for this
equilibrium.
• In 1970, Wanzlick : Imidazolium salts 13a,b could be deprotonated by KOtBu to
afford the corresponding imidazol-2- ylidenes IIIa,b, which were trapped but not
isolated.
 Kinetically protected
 Heteroatom Nitrogens act as σ attractor and π donor (push-pull system)
 Aromaticity is not required for stability (but it helps)
 N-heterocylic carbene is singlet
 Transition metal carbene complex: Alkylidenes

A transition metal carbene complex is an organometallic compound featuring a divalent organic ligand. The
divalent organic ligand coordinated to the metal center is called a carbene; M=CR2
These stability of these carbenes is considered with respect to decomposition or dimerization to olefins.
Unfortunately for Wanzlick, he was never able to isolate a monomeric carbene and he obtained electron-
rich olefins (ERO) instead.

The difference between the results of Arduengo and Wanzlick was interpereted by some researchers to indicate that the steric
bulk and “aromaticity” of Arduengo’s compound was necessary for the isolation of a stable carbene.
The need for bulky substituents was refuted by Arduengowith his synthesis of a carbene with only methyl
substituents on the heterocycle (Arduengo, JACS, 1992, 114, 5530).

The need for “aromaticity” was refuted by Arduengowith his synthesis of a carbene with a saturated
backbone (Arduengo, JACS, 1995, 117, 11027).
The need for the carbenic center to be part of a heterocyclic system was disproven by Alder’s synthesis
of C(NiPr2)2 (Alder, Angew. Chem., Int. Ed., 1996, 35, 1121). This means that the electronic stabilization
of such carbenes by the bis-amido substitution pattern makes for remarkably stable singlet carbenes.
Note that the acyclic examples need at least some steric bulk or they will dimerize.

Overall, it is found that one amido substituent is capable of stabilizing the carbene if the other substituent is a heteroatom
such as S, sometimes O (Alder, JACS, 1998, 120, 11526), and even appropriate aryl groups (Bertrand, Science, 2001,
292, 1901) in both cyclic and acyclic systems.