Chemistry of Polynuclear Cationic Gold(I) Thiolates of Formula [Au 2 (S t Bu)(L 2 )][BF 4 ]

The reactivity of the gold(I) cationic complexes [Au 2 (S t Bu)(L 2 )][BF 4 ] {L = PMe 3 , PEt 3 , P t Bu 3 ; L 2 = dppe [dppe = 1,2‐bis(diphenylphosphanyl)ethane]} was studied. These complexes undergo cleavage of the Au–Au bonds by reaction with phosphanes to give quantitative yields of [Au(S t Bu)(L) n ] and [Au(L) n ][BF 4 ] ( n = 2 or 3) in the case of monodentate phosphanes, and [Au 2 (S t Bu) 2 (dppe)] and [Au(dppe) 2 ][BF 4 ] in the case of the dppe derivative. These compounds also react with [Au(S t Bu)(L)] and exchange the neutral moiety bonded to the [Au(L)] + cation. In both cases some indication of the nature of the intermediates was reached by mass spectrometry (ESI) and NMR spectroscopy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)