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The coordination chemistry of simple phospholes. Complexes of rhenium, ruthenium, cobalt, rhodium and iridium chlorides and of some chlorocarbonyls of ruthenium and rhodium
Author(s) -
Holah David G.,
Hughes Alan N.,
Hui Benjamin C.,
Tse PuiKwan
Publication year - 1978
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570150801
Subject(s) - chemistry , rhodium , phosphole , ruthenium , rhenium , iridium , medicinal chemistry , osmium , metal , cobalt , oxidative addition , transition metal , stereochemistry , inorganic chemistry , photochemistry , catalysis , organic chemistry
The reactions of 1‐phenylphosphole (PP), 3‐methyl‐1‐phenylphosphole (mPP), 3,4‐dimethyl‐1‐phenylphosphole (dPP) and, in certain instances, 1‐ n ‐butyl‐3,4‐dimethylphosphole (dBP) with some transition metal chlorides and some metal‐Cl‐CO systems are reported. These reactions show that simple phospholes in general unexpectedly behave much like ordinary tertiary phosphines and that, unlike the reactions with Ni(II), Pd(II) and Pt(II), the complexes formed are conventional in most respects. However, a few unusual reactions were observed. For example, mPP partially reduces Ru(III) to give a mixed‐valent Ru(III)‐Ru(II) complex while PP reduces Ir(III) to Ir(I). From infrared spectroscopic studies of the square‐planar Rh(I) complexes L 2 Rh(CO) Cl (L = phosphole), it appears that donor character decreases with decreasing substitution on the phosphole ring carbon atoms. Phosphorus‐phenyl cleavage has been observed in reactions of 1‐phenylphosphole with Rh‐CO systems. The results are briefly discussed in relation to the behaviour of other phospholes in similar reactions and in the context of the electronic structure of phospholes.