The Carbenes:

A carbene may be defined as a mononuclear, divalent, Carbon(II) compound.

Carbenes are generally considered as one of the most short lived species in
laboratory, however they can exist as stable entity in the interstellar medium.

Have played an important role as transient species since last six

decades starting from its introduction by Doering in 1950’s.

:CH2 exists as triplet ground state.

 Carbenes

 smallest thinkable carbene Dumas et al. Ann. chim. Phys. 1835, 58, 5-74.

“Now it will be my next task to prepare methylene or derivatives of it which

are free of nitrogen; a number of observations already suggest that such
substances can exist…”
J. U. Nef et al. Justus Liebigs Ann. Chem. 1897, 298, 202-

374.
2
 Singlet or Triplet?

Bertrand and Coworkers Chem. Rev. 2000, 100, 39-91

Mesomeric Effect
R. Hoffmann determined at least 2
ev difference to stabilize carbene
singlet ground state

Kinetic Effect
1962 First N-Heterocyclic carbene

Wanzlick Equilibrium

H. -W. Wanzlick, Angew. Chem., Int. Ed., 1962, 1, 75-80.

5
 The First Stable Carbene

1988

(Phosphino)silyl
carbene

 first isolable carbene

 stabilized by adjacent phosphorus and silicon

substituents

Bertrand et al. J. Am. Chem. Soc., 1988, 110, 6463–6466.

carbene proved to be poor ligand due to strong P-Ccarbene multiple bond character
6
 The First Bottle-able and Isolable Carbene

 First crystalline carbene Colourless

solid
 Crystallized in toluene at low temp

 Stable in air and moisture-free conditions

Demonstrated that free carbenes are not invariably reactive, unstable
reaction intermediates.
Arduengo III et al. J. Am. Chem. Soc., 1991, 113, 361–363.

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 Growth of N-Heterocyclic Carbene Chemistry

SciFinder search as obtained on 17.07.2022. Search results were taken as entered for the topic ‘‘N-heterocyclic carbene’. Document type
was refined to Journal and Review. Duplicates were removed. Results were analyzed by the publication year and exported.

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Why Singlet Carbene is Important in Catalyst Design?

NHC salt is stable (which is used for metal catalyst development),

it has two electrons for donation to metal orbital.
It has empty orbital to accept electron
Hence NHC can be considered as ambiphilic in nature
NHC in catalysis

10
 NHC in Grubbs Catalyst

Robert H. Grubbs:
Nobel Prize in 2005
Grubbs II is catalytically more active than Grubbs
I

Grubbs et al. Org. Lett., 1999, 1, 953–956.

11
An Overview on N-heterocyclic Carbene

Glorius, Nature, 2014, 510, 485-496.

12
 Classification of NHCs

Classical Carbenes

Non-Classical Carbenes

13
 Inspiration from the Interstellar Space

Magnesium (I): Silicon(II): Silicon(I):

Magnesium cyanide (MgCN) Silicon monoxide(SiO) Silicon cyanide (SiCN)
Magnesium isocyanide(MgNC) Silicon monosulfide(SiS) Silicon isocyanide(SiNC)
 Reversing Chemical Property: Nucleophilic Boron!
Angry Pair Effect!
Group 13 elements Lewis Acceptor

Elements Electronic config.

B [He]2s22p1
Al [Ne]3s23p1
Ga [Ar]3d104s24p1
In [Kr]4d105s25p1 Dimerization of BH3

Tl [Xe]4f145d106s26p1 (Nobel Prizes in Chemistry

1976 W Lipscomb and
Inert Pair Effect 1979 HC Brown)

B(I) compounds with an active pair of electrons :

RB:(I) ---(Borylene)----
 Protecting the Unstable Species

N N N
Cl
Mg Mg Si Si
Cl
N N N

Science 2007, 318, 1754–1757 Science 2008, 321, 1069–1071.

(steric protection) (steric and electronic stabilization)
Advantage of Carbene: Electronic synergy
 Stabilization of Different Oxidation State

Schleyer, Robinson and coworkers

Science 2008, 321, 1069-1071
Mandal and Roesky Chem.
Commun. 2010, 46, 6016–6041
(Highlighted on front cover)
Power, Nature, 2010, 463, 171-177

Power and co-workers Science 2009,

325, 1668–1670.

Braunschweig and co-workers Science

2018, 359, 896-900

Bertrand and coworkers Science 2007, 316, 439-441

 R New Normal
Turn N-heterocyclic
in NHC Chemistry: Year 2009
carbene, developed by Arduengo et al
N (J. Am. Chem. Soc. 1991, 113, 361–363)

N
R
R
N

N
R
Chem. Commun., 2001, 2274–2275
Isolated abnormal N-heterocyclic (Crabtree , Faller and coworkers)
carbenes (also called non classical
carbenes) were considered elusive
species and in 2009…
 Bertrand and coworkers Science 2009, 326, 556-559

“Normal carbenes rapidly became a key tool for organometallic chemistry and organic
synthesis once they were available as stable free ligands some 20 years ago. Given the
unique impact of abnormal carbenes on the reactivity of transition metals, the
accessibility of free abnormal carbenes may become another cornerstone in this field,
and it will be exciting to witness developments in these directions.”
Martin Albrecht, Science 2009, 326, 532-533
 NHC’s are very good donors and aNHC’s are even better!

• N-heterocyclic carbenes (NHCs) represent a particularly attractive class of

ligands for such applications, since they belong to the class of the
strongest neutral donors known.
R R
N N

N N
R R
Application of newly Reported Abnormal N-heterocyclic Carbene:
1. As organocatalyst since it will be better nucleophile than normal NHCs.
2. As building block for organometallic catalysts since Abnormal N-
heterocyclic Carbene will have better metal holding capacity will result no
leaching and catalyst poisoning.
 Global CO2 emission in last 20 years

IEA, Annual change in global energy-related CO2 emissions, IEA, Paris

23
 Global Energy Balance (2015)

Coa
Oil
l

Natural
gas

IEA, Annual change in global energy-related CO2 emissions, International Energy Agency (IEA
24
Paris
CCS and CCU

25
Reactions with CO2

Known
 Current status and major challenges

Only 7-10 % CO2 is chemically converted

 Thermodynamic stability of CO2

 Metal based catalysts are required to activate CO 2

 Harsh Condition

 Expensive and toxic

 Energy intensive Process

How to avoid?

Metal free catalyst 27

Carbene as Metal-free Catalyst

28
 Learning from Nature

Nucleophilic activation!!

29
 Interaction of CO2 with metals

How to mimic metals for CO2 activation!!

30
CO2 activation by nucleophiles

Villiers et al. Angew. Chem., Int. Ed., 2010, 49,

3465-3468.
31
 Fuel from Air

David W. Keith,
Science, 2009, 325, 1654-1655.

‘Coming from fuel and returning to fuel’

G. A. Olah,
Angew. Chem., Int. Ed., 2013, 52,
104 – 107.
Prakash and Olah JACS 2016, 138, 778-
781
(homogeneous CO2 capture from air
under drastic conditions)

32
Metal free CO2 reduction from air

Mandal et al. Chem. Sci. 2019, 10, 1879-1884

33
 Arresting CO2 from Air and its Reduction under
Ambient Conditions

Air Air
(0.039 % CO2) (0.039 % CO2)
Metal Free Meta Free Formate
Compound (Metal Free Catalyst 2)
(CO2 from Air) -H2
Solvent, Hydride
12 h Confirmed by single crystal Source,
X-ray Crystallography 3 h

CH3OBR2
Confirmed with
1H, 13Cand 11B NMR
Experiment

Confidential
Metal free catalysts for CO2 reduction

Chem. Sci., 2020, 11, 10571-10593

35