Coordination chemistry of arylphosphanes:binding and interligand interactions in chromium, molybdenum and tungsten carbonyl complexes
Abstract The first part of this work consisted of a study of the coordination chemistry of aromatic (P,S) and (P,O) heterodonor phosphanes with Cr(CO) 6 , Mo(CO) 6 and W(CO) 6 . The (P,S) donor ligands having one or two o -thiomethoxyphenyl groups, preferred bidentate coordination mode, while t...
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| Format: | Doctoral Thesis |
| Language: | English |
| Published: |
University of Oulu
2001
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| Online Access: | http://urn.fi/urn:isbn:9514259866 http://nbn-resolving.de/urn:isbn:9514259866 |
| Summary: | Abstract
The first part of this work consisted of a study of the coordination chemistry of aromatic (P,S) and (P,O) heterodonor phosphanes with Cr(CO)
6
, Mo(CO)
6
and W(CO)
6
. The (P,S) donor ligands having one or two
o
-thiomethoxyphenyl groups, preferred bidentate coordination mode, while the (P,O) donor ligands, having one, two or three
o
-methoxyphenyls, formed monodentate phosphorus bound complexes. Steric and electronic parameters affecting the coordination chemistry of the phosphanes are discussed for the monodentate complexes.
In the second part, triphenylphosphane and 2- and 4-pyridyldiphenylphosphane substituted tungsten tetracarbonyl
derivatives was prepared, and attractive intramolecular interactions between the phosphane ligands were studied for
both the neutral and the protonated complexes. Hydrogen bonding, π
-stacking and cation-π
bonding interactions were established, and observed to influence the
cis/trans
isomerism of the complexes.
Cis/trans
isomerism could be tuned by protonation, and deprotonation of the pyridyldiphenylphosphane derivatives.
All the complexes were characterised by
1
H,
13
C-{
1
H} and
31
P-{
1
H} NMR spectroscopy, X-ray crystallography, IR spectroscopy, and either elemental analysis or mass spectroscopy.
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