Nitrogen monoxide

&
Dinitrogen
ASHKWINEE A/P SIRAMALLO 173347
SITI SAKINAH BINTI YUSOF 174507
SITI NOOR HANIS FARIHAH BINTI MOHSIN 174228
FARA ADELINA BINTI MOHAMAD ROSLAN 175271
NUR IWANI BINTI ZAKARIA 172717
 Nitrogen monoxide (NO)
• Nitric oxide,
• Free NO is a stable free radical because the
ON−NO bond in the dimer is very weak.
• 11 valence electrons
• Bonded NO known as Nitrosyl ligand
• Bound in 1 of 2 modes to d-metal atoms
• Bent or linear
• In complexes, NO can change coordination mode:
• Linear Bent
• Reduces number of e- on metal by 2
LINEAR MODE
 NO as cation (NO+)
 NO+ isoelectronic with CO,
 Thus the bonding between a NO+ and
metal follows the same principles as the bonding in CO complexes.
 2e- σ donor with strong π-acceptor ability
 behave as the 2e- donor NO+ on the ionic model & 3e- ligand on the
covalent model

BENT MODE
 NO as anion (NO-)
 NO- donate 2e- to metal
 same numbers of e- or
same electronic structure

NO+ isoelectronic with CO

 Dinitrogen (N2)
• Complexes have a terminal monohapto link, η1 – N
which bonding considered to be isoelectronic CO
ligand.
• Both weaker σ donor and weaker π acceptor than CO
hence bound less strongly.
*only good π-donor metal atoms bind N2
• Participate in 2 bonding interactions and bridge two
metal atoms.
– Occasionally found bound in a dihapto (η2) side-on
fashion.
 COMMON NITROSYL SYNTHETIC
METHODS
1. NITROSYLATION BY NO+ DONORS
Ligand displacement by NO+ delivery agents
such as [NO+ ]BF4 after addition of NO gas, to
displace a solvent molecule.
Treating metal carbonyl complexes with
(NO)PF6 or (NO)BF4, allows for substitution of
CO by the isoelectronic NO+ ligand。
2. DIRECT ADDITION OF NO GAS
 Direct addition of nitric oxide gas is a
convenient method of preparing transition
metal nitrosyl complexes。
nitric oxide gas degrades to N2O and NO2
under pressure and must be purified prior to
use under an inert atmosphere.
For example； synthesis of iron nitrosyl
complexes
Figure：Nitrosylation by NO Donors and Direct Addition of NO Gas
 SYNTHESIS OF DINITROGEN/N2
COMPLEXES
• Of two M-N interactions, back donation is
important for stability
• Only strongly π-basic metals bind N2
• Because two ends of N2 are the same, the
molecule can easily act as bridging ligand between
two metals
• Examples of complexes in which the N2 bridges two
metals
e.g.:

e.g.:
Common preparative routes:
1. Reduction of a phosphine-substituted metal
halide in the presence of N2

e.g.: synthesis of molybdenum-nitrides complexes

2. Degradation of nitrogen-containing ligand

e.g.:
3. Displacement of a labile ligand by N2

e.g.:
 SPECIAL CHARACTERISTIC
1. Nitrogen monoxide
React with all transition metals – metal nitrosyls
Most common bonding mode – linear (M – NO)
Two types of metal nitrosyls :-
Linear (triple bond) | (1525 – 1690 cm-1 )
Bent (double bond) | (1650 – 1900 cm-1 )
*it can be distinguished using infrared spectroscopy

Also can act as bridgind ligand

Ligand that connects two or more atoms ; usually metal ions
2. Dinitrogen
Act as bridging ligand between two metals

Has a high bond enthalpy due to the N = N bond

It is both weaker  donor and weaker  acceptor

Mainly used in the industrial manufacturing of

compounds (ammonia and calcium cynamide)

Also used in the manufacturing industries such as

iron and steel – to obtain inert atmosphere
 References:
• Crabtree, H. (2005) The Organometallic Chemistry of the Transition
Metals. 4th edition. Yale University, John Wiley & Sons, Inc., Publication,
Hoboken New Jersey
• Nitrogen Fixation (1971)
http://pubs.rsc.org/en/content/articlepdf/1972/CS/CS9720100121
• Nitrogen Fixation and Dinitrogen Complexes (2007)
http://chem.sci.utsunomiya-u.ac.jp/cejrnlE.html
• Tanaka & Arashiba (2014). Unique behaviour of dinitrogen-bridged
dimolybdenum complexes bearing pincer ligand towards catalytic
formation of ammonia. Page 1-3.