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Amity University Rajasthan: Nitrosyl

This document discusses nitrosyl complexes, which contain the nitrosonium (NO+) ligand. NO+ can bind in either a linear or bent geometry, determining whether it acts as a 3-electron or 1-electron donor. The electronic structure of NO makes it susceptible to oxidation and reduction. Nitrosyl complexes are commonly assumed to contain NO+ but can also contain NO. or NO-. Establishing the identity of the coordinated NO ligand requires various physical methods and theoretical calculations. NO can also serve as a bridging ligand between multiple metal centers.

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136 views12 pages

Amity University Rajasthan: Nitrosyl

This document discusses nitrosyl complexes, which contain the nitrosonium (NO+) ligand. NO+ can bind in either a linear or bent geometry, determining whether it acts as a 3-electron or 1-electron donor. The electronic structure of NO makes it susceptible to oxidation and reduction. Nitrosyl complexes are commonly assumed to contain NO+ but can also contain NO. or NO-. Establishing the identity of the coordinated NO ligand requires various physical methods and theoretical calculations. NO can also serve as a bridging ligand between multiple metal centers.

Uploaded by

gul
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Amity university

Rajasthan
Subhrangsu Sekhar Dey

Nitrosyl
Nitrosyls

 NO is a stable free radical


 Also as NO+ in NOBF4
 NO+ is isoelectronic with CO
 It can bind as NO+ and it will be three electron donor
 When NO is bent then it will be one electron donor
 NO is a fifteen electron molecule
 with one unpaired electron residing in the π* molecular orbital:
(σ1)2(σ1*)2(σ2)2(σ2*)2(σ3)2(πx, πy)4(πx*, πy*)1(σ*3)

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


particularly the formation of nitrosonium cation (NO+) on oxidation and the reduction to
nitroxide anion (NO–), making it a "non-innocent" ligand. C.K. Jørgenson first described ligands
as "innocent" and "suspect": "Ligands are innocent when they allow oxidation states of the
central atoms to be defined. The simplest case of a suspect ligand is NO.

 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, magnetic circular dichroism (MCD), etc., and
theoretical calculations.
NO Bonding

 NO binds in two ways


 Either as NO+ then it will give linear
molecule and will be three electron
donor

 Or as NO- then it will give bent


molecule and will be one electron
donor ..
 [Co(en)2(NO)Cl]+, with seven electrons
M N
of pi-symmetry (six in t2g orbitals and
one on NO), adopts a bent NO ligand O
 Whereas [Fe(CN)5(NO)]3−, with six
electrons of pi-symmetry, adopts a M N O
linear nitrosyl.
The nitrosyl cation serves as a two-electron donor to the metal and
accepts electrons from the metal via back-bonding Nitric oxide can also
serve as a bridging ligand. In the compound [Mn3(η5C5H5)3 (μ2-NO)3 (μ3-
NO)], three NO groups bridge two metal centres and one NO group bridge
to all three.

CoCl(en)2NO
Bridging 3D-balls
Reaction

When NO+ is added it makes reaction with Nu- more


probable

Mo(CO)2Cp Nu No Reaction

Nu
NOBF4

Nu Mo(CO)(NO)Cp
Mo(CO)(NO)Cp
Electron Count

 When NO change from linear to bent both the number of electron on the
metal and the oxidation state of the metal will change
 CoCl2L2(lin-NO)
 CoCl2L2(bent-NO)
Electron Count
Preparation
- NO+ is a powerful oxidation agent
- Migratory insertion is also possible for NO
Application
Metal-catalyzed reactions of NO are not commonly synthetically useful. Nitric
oxide is however an important signalling molecule in nature and this fact is the
basis of the most important applications of metal nitrosyls.
The nitroprusside anion, [Fe(CN)5NO]2−, a mixed nitrosyl cyano complex, has
pharmaceutical applications as a slow release agent for NO.
The signalling function of NO is effected via its complexation to haeme proteins,
where it binds in the bent geometry.

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