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(Triphenylphosphane)gold(I) Scrambling in a Hexanuclear Complex of Phenylene‐1,2‐bis(phosphane)
Author(s) -
Assmann Bernd,
Schmidbaur Hubert
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300212
Subject(s) - chemistry , scrambling , tetrafluoroborate , dichloromethane , oxonium ion , phosphide , intramolecular force , phosphine , phenylene , crystallography , gold compounds , stereochemistry , ion , organic chemistry , ionic liquid , metal , catalysis , philosophy , linguistics , polymer , solvent , combinatorial chemistry
Phenylene‐1,2‐bis(phosphane) reacts with two mole‐equivalents of tris[(triphenylphosphane)gold(I)]oxonium tetrafluoroborate in dichloromethane at −78°C to give high yields of a hexanuclear complex {C 6 H 4 ]P(AuPPh 3 ) 3 ] 2 } 2+ · 2 BF‐ 4 ( 1 ). The variable‐temperature 31 P{ 1 H}‐NMR spectra of the product in CD 2 Cl 2 at ‐ 80°C are compatible with a static structure featuring three Ph 3 PAu units associated with each of the two C 6 H 4 P 2 phosphide functions, as derived from a clear doublet/quartet pattern. At 50°C in CDCl 3 , however, there is rapid intramolecular scrambling of these Ph 3 PAu units, which gives rise to a triplet/septet pattern with the J (P,P) value reduced to exactly one half of the value at the low temperature limit.