Abstract:
The present interest in organometallic nitrosyl complexes stems partly
from their similarity with carbonyl analogues which are widely used as
catalysts in industrial processes. The search for potential new catalysts
among nitrosyl complexes is perhaps not surprising when it is realised that
the nitrosonium ion (NO+), the species normally regarded as being co-ordinated,
is isoelectronic with carbon monoxide. Further interest may be due to the
fact that NO+ is also isoelectronic with molecular nitrogen and hence nitrosyl
complexes may be suitable as models for co-ordinated nitrogen in the process
of nitrogen fixation. In their own right nitrosyl complexes pose problems
of chemical interest concerned with their structure and the bonding associated
with the metal-nitrosyl bond.
As part of an investigation into the geometry of co-ordinated nitrosyl
this thesis presents structural data for several nitrosyl complexes of Group
VIII metals .. In addition the mode of binding of the isocyanide group has
been studied as well as the associated stereochemistry of the metals ruthenium,
osmium and iridium.
To date, structural studies have established three different modes
of co-ordination for the nitrosyl group. Probably the most common involves
a linear arrangement of metal, nitrogen and oxygen, the effective coordinating
species being regarded as the diamagnetic nitrosonium ion (NO+).
