Different Coordination Modes of a Tripod Phosphine in Gold(I) andSilver(I) Complexes

摘要

The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au3(tripod)X3 [X = Cl(>1), Br(>2), I(>3)]; [Au3(tripod)2Cl2]Cl (>4); Au(tripod)X [X = Br(>5), I(>6)]; Ag3(tripod) (NO3)4 (>7), Ag(tripod)NO3 (>8). They were characterized by X-ray diffraction (complexes >2, >3 and >4), ³¹P NMR spectroscopy, electrospray and FAB mass spectrometry and infrared spectroscopy. Complexes >2 and >3 show a linear coordination geometry for Au(I), with relatively short Au-P bond distances. Complex >3 has a Au•••Au intramolecular distance of 3.326 A °,while complex >2 had a short Au•••Au intermolecular interaction of 3.048 A °. Complexes >4-6 were found by³¹P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as[Au3(tripod|)2Cl2]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), thefirst example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au3(tripod)Cl3] (>1)with tripod led successfully to the formation of [Au3(tripod|)2Cl₂]⁺ and [Au₃(tripod)₂Cl₃]⁺ and [Au₃(tripod|)₃Cl]²⁺. The silver(I)complexes, >7 and >8 appear to contain linear and tetrahedral Ag(I), respectively.