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Synthesis, X‐ray Crystal Structures and Reactivity Towards Alkynes of Gold(I)–Phosphinine Complexes
Author(s) -
Mézailles Nicolas,
Ricard Louis,
Mathey François,
Le Floch Pascal
Publication year - 1999
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/(sici)1099-0682(199912)1999:12<2233::aid-ejic2233>3.0.co;2-2
Subject(s) - chemistry , cationic polymerization , alkyne , cycloaddition , crystal structure , ligand (biochemistry) , trimethylsilyl , crystallography , crystallization , ring (chemistry) , derivative (finance) , stereochemistry , medicinal chemistry , catalysis , polymer chemistry , organic chemistry , biochemistry , receptor , financial economics , economics
The coordination behaviour of 2,6‐disilyl‐substituted phosphinines towards gold(I) has been examined. The reaction of the bis(trimethylsilyl)phosphinine 1 with [AuCl(SMe 2 )] gives the corresponding AuCl derivative 2 . X‐ray crystal structure analysis reveals that the aromaticity of the phosphinine ring is slightly reduced as a result of the poor π‐back bonding ability of the AuCl fragment. The same phenomenon is observed in the cationic complex [Au( 1 ) 2 ][GaCl 4 ] ( 3 ) which was readily prepared by reaction of two equivalents of 1 with [AuCl(SMe 2 )] followed by treatment with GaCl 3 at low temperature. Reaction of 2,6‐bis(phenylethynyldimethylsilyl)phosphinine ( 4 ) with the same precursor leads similarly to the complex [AuCl( 4 )] ( 5 ). Interestingly, this complex dimerizes upon crystallization to give the bis(phosphabarrelene) complex 6 , also structurally characterized. The formation of 6 results from a [4 + 2] cycloaddition between one alkynyl group of each phosphinine with the other phosphinine subunit. The formation of the cationic complex [Au( 4 )][GaCl 4 ] ( 8 ) occurs under classical conditions but it disproportionates to give the cationic complex [Au( 4 ) 2 ][GaCl 4 ] ( 9 ) and colloidal gold deposition. The formation of 9 has been ascertained by treating 8 with one equivalent of ligand 4 . Additionally, 9 can also be obtained in a straightforward fashion by treating two equivalents of 4 with [AuCl(SMe 2 )] followed by treatment with GaCl 3 at low temperature. The structure of 9 has been elucidated. Despite a particular arrangement of the alkyne groups which encapsulate the gold coordination sphere, no gold–alkyne interactions are visible.