University of Oulu

Coordination chemistry of arylphosphanes : binding and interligand interactions in chromium, molybdenum and tungsten carbonyl complexes

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Author: Hirsivaara, Leeni1
Organizations: 1University of Oulu, Faculty of Science, Department of Chemistry
Format: ebook
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 0.9 MB)
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Language: English
Published: 2001
Publish Date: 2001-05-14
Thesis type: Doctoral Dissertation
Defence Note: Academic Dissertation to be presented with the assent of the Faculty of Science, University of Oulu, for public discussion in Kajaaninsali (Auditorium L6), Linnanmaa, on June 16th, 2001, at 12 noon.
Reviewer: Professor Markku Leskelä
Professor Kari Rissanen


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 ¹H, ¹³C-{¹H} and ³¹P-{¹H} NMR spectroscopy, X-ray crystallography, IR spectroscopy, and either elemental analysis or mass spectroscopy.

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Series: Acta Universitatis Ouluensis. A, Scientiae rerum naturalium
ISSN-E: 1796-220X
ISBN: 951-42-5986-6
ISBN Print: 951-42-5985-8
Issue: 364
Copyright information: © University of Oulu, 2001. This publication is copyrighted. You may download, display and print it for your own personal use. Commercial use is prohibited.