Doublet (1 Radical, 1 Pair, 1 Vacant Orbital) : A Doublet & A Quartet Spin State Form

Carbynes
Similar bonding formulations as per Fischer & Schrock carbene.

The free carbyne exists in a doublet & a quartet spin state form
doublet (1 radical, 1 pair, 1 vacant orbital) quartet (3 radicals)
• The carbyne ligand is linear

• Carbyne carbon is sp hybridized
• The MC bond is very short (1.65 – 1.90 Å)
Metal Carbynes
A quartet (Schrock) carbyne is

A doublet (Fischer) carbyne is sp hybridized
also sp hybridized
Contains one filled sp orbital capable of donating
Contains three singly occupied
2e- to a metal centre
orbitals capable of forming three
Contains one singly occupied p orbital capable
covalent M-C bonds (one σ &
forming an additional π bond
two π bonds)
The remaining empty p orbital is capable of
3e- ligand in covalent model
M→C π back donation
(or 6e- ionic model)
3e- donor covalent model / 4e- donor ionic model
The M−L multiply bonded systems even extended beyond the doubly bonded
Fischer & the Schrock carbenes to the triply bonded LnM≡CR type Fischer
carbyne & the Schrock carbyne complexes.
1st Carbyne complex

1st Carbene complex
Upon binding to the M in its doublet spin state as in the Fischer carbene system,
the carbyne moiety donates two electrons via its sp hybridized lone pair
containing orbital to an empty metal d-orbital to yield a LnM←CR type ligand to
metal dative bond.
 It also makes a covalent π−bond through one of its singly occupied p z orbital
with one of the metal d orbitals.
The carbyne−metal interaction consist of two ligand to metal interactions
namely
a dative one & a covalent one
In addition to these two types of ligand to metal bonding interactions, there
remains an empty py orbital on the carbyne−C atom that can accommodate
electron donation from a filled metal d orbital to give a metal to ligand π−back
bonding interaction .
Analogously, in the quartet carbyne spin state in the Schrock carbyne
systems 3 covalent bonds occur b/n the singly occupied sp, py & pz orbitals
of carbyne−C moiety with the respective singly occupied metal d orbitals .
Similar to the Fischer carbenes & Schrock carbenes, the Fischer carbyne
complexes are formed with metal centers in lower oxid. States.
E.g. Br(CO)4W≡CMe,
while the Schrock carbyne complexes are formed with metals in higher
Carbyne
ox.state.
complexes can be prepared by the following methods
1. The Fischer carbyne complexes can be prepared by the electrophilic
abstraction of a methoxy group from a methoxy methyl substituted
Fischer
carbene complex.
2. Schrock carbynes can be prepared by the deprotonation of a α−CH bond
of a metal−carbene complex.
3. By an α−elimination reaction on a metal−carbene complex
4. By metathesis reaction
The reactivities of Fischer & the Schrock carbynes mirror that of the Fischer &
Schrock carbenes.
Eg. The Fischer carbyne undergo nucleophilic attack at the carbyne−C atom
while the Schrock carbyne undergo electrophilic attack at the carbyne−C
atom.
N-Heterocyclic Carbenes (NHC’s)
• In contrast to Fischer & Schrock type carbenes, NHC’s are extremely stable,
inert ligands when complexed
• Like phosphine ligands they are electronically & sterically tunable
• Also, like phosphines they are very good σ-donors & promote a wide variety of
catalytic reactions
Other class of Organo-Transition metal complexes
Nitrosyls
 Similar to CO in σ-donor & π-acceptor properties
 NO is a stable free radical
 Also as NO+ in NOBF4
 NO+ is isoelectronic with CO
 It can bind as NO+ & it will be 3e- donor
 When NO is bent then it will be 1e- donor

Electron counting scheme considers
 linear NO complexes as 2 e- NO+
 bent NO complexes as 2 e- NO-
NO Bonding
NO binds in two ways:
• Either as NO+ then it will give linear molecule & will be
3e- donor
M N O
Or
• As NO- then it will give bent molecule & will be 1e- donor
..
M N
O
M.O. of NO
• NO is a 15e- molecule with one unpaired electron residing in the π* MO.
• This electronic configuration explains the high reactivity of the NO molecule,

particularly the formation of nitrosonium cation (NO+) on oxidation & the
reduction to nitroxide anion (NO–), making it a "non-innocent" ligand
• Most of the known stable "nitrosyl" complexes are assumed to contain the
diamagnetic π acceptor ligand nitrosonium, NO+,but there are cases when NO• or
NO– (nitroxide) can be reasonably postulated as ligands in transition metal
complexes.
• Establishing the actual form of coordinated NO often requires a variety of
physical methods such as IR, EPR, NMR, UV/VIS, X-rays, resonance Raman,
etc., and theoretical calculations.
Electron Count
 When NO change from linear to bent both the number of electron on the metal
& the oxidation state of the metal will change
• CoCl2L2(lin-NO) ---- 18e-

• CoCl2L2(bent-NO) ---- 16e-
Compounds of NO
Co(CO)4NO; Mn(CO)4NO; Fe(CO)2(NO)2
EAN? Check
Bent M-NO, with M-N-O bond angle of 110-120◦, then NO is 1 e- donor
N O
M
NO has a very similar M.O. diagram to that of CO, except that it contains one
extra electron in the π* orbital.
O
O O O N
N N N N +L
Fe Fe O O N Fe L
C C C C C C
O O O
O O O
18e- (Fe2  ) 16e- (Feo ) 18e- (Feo )
σ
M N O
π
3 e- are donated to the M.O. scheme of the complex by NO.
In this case L-N-O bond ͠ 170-180◦
NO is a 3e- donor;

:. NO+ is 2 e- donor
i.e. NO+ = CO,
i.e. Isoelectronic
Now when the nitric oxide bonds to the metal form
a linear nitrosyl ,the lone pair on the nitrogen will
bind to the metal to form the sigma bond, this gives
the metal two electrons.
When the occupied d orbitals on the metal interact
with the П* orbitals of the nitric oxide then the
electron in the П* orbitals will be shared with the
metal in the new П bonds between the metal &
the nitrosyl, thus in this way one extra electron is
shared with the metal.
As a result the metal gets a total of 2+1 electrons to
MO diagram for NO add to its valence count, which makes three.

Preparation
NO+ is a powerful oxidation agent
Migratory insertion is also possible for NO
END OF SESSION 7

Doublet (1 Radical, 1 Pair, 1 Vacant Orbital) : A Doublet & A Quartet Spin State Form

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Doublet (1 Radical, 1 Pair, 1 Vacant Orbital) : A Doublet & A Quartet Spin State Form

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Carbynes

Similar bonding formulations as per Fischer & Schrock carbene.

doublet (1 radical, 1 pair, 1 vacant orbital) quartet (3 radicals)

• The carbyne ligand is linear

A quartet (Schrock) carbyne is

1st Carbyne complex

3. By an α−elimination reaction on a metal−carbene complex

 NO is a stable free radical

 Also as NO+ in NOBF4

 NO+ is isoelectronic with CO

 It can bind as NO+ & it will be 3e- donor

 When NO is bent then it will be 1e- donor

• This electronic configuration explains the high reactivity of the NO molecule,

• CoCl2L2(lin-NO) ---- 18e-

NO is a 3e- donor;

MO diagram for NO add to its valence count, which makes three.

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