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Lithium Salts of 2,4,6‐Triaryl‐λ 4 ‐phosphinine Anions – A Comparison Study
Author(s) -
Bruce Marlene,
Meissner Gisa,
Weber Manuela,
Wiecko Jelena,
Müller Christian
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201301259
Subject(s) - chemistry , denticity , phenyllithium , lone pair , lithium (medication) , chelation , ligand (biochemistry) , medicinal chemistry , coordination complex , hydrolysis , metal , inorganic chemistry , stereochemistry , molecule , organic chemistry , receptor , medicine , biochemistry , endocrinology
The λ 3 ‐phosphinine derivatives 2,6‐diphenyl‐4‐( p ‐tolyl)phosphinine and 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine were quantitatively converted into the corresponding λ 4 ‐phosphinine anions by reaction with phenyllithium. Systematic hydrolysis experiments with H 2 O and MeOH show that a subtle interplay between the p K a values of the generated 1,2‐dihydrophosphinine derivatives and the p K b value of the formed bases, LiOH and LiOCH 3 , respectively, leads either to the kinetic or thermodynamic product. The coordination chemistry of the λ 4 ‐phosphinine anions towards Rh I was further investigated, and the anions based on 2,6‐diphenyl‐4‐( p ‐tolyl)‐phosphinine and 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine demonstrate different coordination modes. Whereas the former coordinates in an η 5 fashion towards the Rh I atom, the latter acts as a bidentate chelating ligand with an η 1 coordination to the metal center through the phosphorus lone pair.