1st

The first nitrosyl complex was discovered in 1790 by J. Priestley ([Fe(H2O)5(NO)]2+). This
complex is also formed in the qualitative test for nitrate with ferrous sulfate and sulfuric acid
(“brown ring test”).Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded
to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and
coligand.Most complexes containing the NO ligand can be viewed as derivatives of the nitrosyl
cation, NO+ . The nitrosyl cation is isoelectronic with carbon monoxide, thus the bonding between a
nitrosyl ligand and a metal follows the same principles as the bonding in carbonyl complexes. The
nitrosyl cation serves as a two-electron donor to the metal and accepts electrons from the metal via
back-bonding. In an alternative description, nitric oxide serves as a 3-electron donor, and the metal-
nitrogen interaction is a triple bond.
There are different types of nitrosyl ligand-bridging ligand,Linear and bent NO ligand.These
can be distinguished using infrared spectroscopy. Linear M-N-O groups absorb in the range
1525–1690 cm−1 , whereas bent nitrosyls absorb in the range 1650–1900 cm−1 . The differing
vibrational frequencies reflect the differing N-O bond orders for linear (triple bond) and bent
NO (double bond).Bent nitrosyl groups (N-O double bond) absorb in the range 1525–1690
cm−1.
Here we will use the Enemark-Feltham notation.This is used to describe the number of d-type
electrons present in a complex. It is deliberately ambiguous, because the true oxidation state
of a metal coordinated by non-innocent ligands is often unclear. When written with this
notation, the d-electron count is always consistent no matter how the nitrosyl ligands are
treated (i.e. NO+ , NO·, or NO− ).

In this experiment we will synthesisze Iron Nitrosyl Complex [Fe(NO)(S2CNEt2)2]. First time
this complex was first reported in 1931 by L.Cambi and Cagnasso. This complex contains the
bidentate sulphur ligand diehtyldithiocarbamate,In this comples we will investigate the nature of
the bonding of the NO ligand.Increasing strength of the π-back bond strengthens the M-N bond and
weakens the N-O bond.That is reflected in the IR stretching frequencies.Complex was
synthesized by the reaction of ferrous sulfate with nitrous acid in the presence of a dithiocarbamate
ligand.The reaction of the nitrite with sulfuric acid generates the nitrous acid (HNO2) in-situ, which
is reduced by Fe2+ to yield nitric oxide, which reacts with the iron aquo complex to form
[Fe(H2O)5(NO)]2+.The addition of the dithiocarbamate ion leads to the formation of the dark-
green Fe(NO)dtc2.
Metal-nitrosyls are assumed to be intermediates in catalytic converters, which reduce the emission
of NOx from internal combustion engines. This application has been described as “one of the most
successful stories in the development of catalysts.”
 2nd
The first nitrosyl complex was discovered in 1790 by J. Priestley ([Fe(H2O)5(NO)]2+).Metal
nitrosyl complexes, have gained significant interest in the past twenty years because of the
important role nitric oxide displays as signaling molecule in biological systems.Metal nitrosyl
complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Nitric oxide
(NO) is a colorless gas that is thermodynamically unstable. Due its odd number of electrons, the
compound is paramagnetic.The nitrosyl cation is isoelectronic with carbon monoxide, thus the
bonding between a nitrosyl ligand and a metal follows the same principles as the bonding in
carbonyl complexes. The nitrosyl cation serves as a two-electron donor to the metal and accepts
electrons from the metal via back-bonding.

In metal nitrosyl complexes, nitric oxide (NO) is bonded to a metal. The nitrosyl ligand can act as a
one-electron or a three-electron donor. The nitrosyl cation (:NO:+) can use its lone pair on the
nitrogen atom to form a bond to the metal atom like its isoelectronic conterparts the carbonyl (:C
O:) and the cyanide (:C N:−). Like carbonyl ligands, here we can see various degrees of π-back
bonding (NO+ is a stronger π-acceptor than CO).Increasing strength of the π-back bond strengthens
the M-N bond and weakens the N-O bond.Here we will use the Enemark-Feltham notation.This
is used to describe the number of d-type electrons present in a complex. It is deliberately
ambiguous, because the true oxidation state of a metal coordinated by non-innocent ligands is
often unclear. When written with this notation, the d-electron count is always consistent no
matter how the nitrosyl ligands are treated (i.e. NO+ , NO·, or NO− ).

The unpaired electron of the free NO resides in a π∗ orbital and is easily removed to give
NO+, which acts as a stronger -acceptor. The antibonding character of the unpaired electron
is reflected in the IR stretching frequencies.Free absorb near about 1876 cm−1. Linear M-N-O
groups absorb in the range 1525–1690 cm−1 , whereas bent nitrosyls absorb in the range 1650–
1900 cm−1.

In this experiment, nitrosyl complex of iron synthesized also contains the bidentate sul-phur ligand
diehtyldithiocarbamate, and investigate the nature of the bonding of the NO ligand in it.First time
this complex was first reported in 1931 by L.Cambi and Cagnasso.Complex was synthesized by
the reaction of ferrous sulfate with nitrous acid in the presence of a dithiocarbamate ligand.The
reaction of the nitrite with sulfuric acid generates the nitrous acid (HNO2) in-situ, which is reduced
by Fe2+ to yield nitric oxide, which reacts with the iron aquo complex to form
[Fe(H2O)5(NO)]2+.The addition of the dithiocarbamate ion leads to the formation of the dark-
green Fe(NO)dtc2.

References

Hayton, T. W.; Legzdins, P.; Sharp, W. B. (2002). "Coordination and Organometallic

Chemistry of Metal-NO Complexes". Chem. Rev. 102 (1): 935–991. doi:10.1021/cr000074t.
PMID 11942784.
• Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. pp. 447–453. ISBN 0-08-037941-9.
• Enemark, J. H.; Feltham, R. D. "Principles of structure, bonding, and reactivity for metal
nitrosyl complexes". Coord. Chem. Rev. 1974 (13): 339–406. doi:10.1016/S0010-
8545(00)80259-3.
• Max Herberhold, Abbas Razavi "Tetranitrosylchromium [Cr(NO)4]" Angewandte Chemie
International Edition in English, 1972, Volume 11, pages 1092–1094.
doi:10.1002/anie.197210921
• Richard R. Thomas, Ayusman Sen. "Acetonitrile Complexes of Selected Transition Metal
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• Kaspar, Jan; Fornasiero, Paolo; Hickey, Neal (2003). "Automotive Catalytic Converters:
Current Status and Some Perspectives". Catalysis Today. 77: 419–449. doi:10.1016/S0920-
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