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Steric and electronic effects on 195Pt NMR chemical shifts of platinum (II) phosphine complexes

✍ Scribed by Howard C. Clark; A. Martin de P. Nicholas

Publisher
John Wiley and Sons
Year
1990
Tongue
English
Weight
404 KB
Volume
28
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

Platinum‐195 chemical shift measurements for cis‐PtCl~2~(PCy~3~)~2~ and trans‐PtXCl(PCy~3~)~2~ (X = H, Cl, SnCl~2~Ph and SnCl~3~) in methylene chloride solution are reported. A comparison of these shifts with those from analogous complexes containing less bulky phosphine ligands indicates significant steric effects on the ^195^Pt shift of the PCy~3~ complexes. For __cis‐__PtCl~2~(PCy~3~)~2~ a downfleld shift of over 200 ppm is obtained. For the __cis‐__PtCl~2~(PCy~3~)~2~ complexes the deshielding of ^195^Pt is found to increase in the order X = H < Cl < SnCl~3~, SnCl~2~Ph, which corresponds to the change in the bulk of X. The observed downfield shifts in the bulky ~2~Ph complexes are rationalized in terms of steric crowding, lengthening of the PPt bond and deshielding of the Pt nucleus.

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