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

The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au(3)(tripod)X(3) [X = Cl(1), Br(2), I(3)]; [Au(3)(tripod)(2)Cl(2)]Cl (4); Au(tripod)X [X = Br(5), I(6)]; Ag(3)(tripod) (NO(3))(4) (7), Ag(tripod)NO(3) (8). They were characterized by X-ray diffraction (complexes 2, 3 and 4), (31)P 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 degrees , while complex 2 had a short Au Au intermolecular interaction of 3.048 A degrees . Complexes 4-6 were found by (31)P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as [Au(3)(tripod|)(2)Cl(2)]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), the first example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au(3) (tripod)Cl(3)] (1) with tripod led successfully to the formation of [Au(3)(tripod|)(2)Cl(2)](+) and [Au(3)(tripod)(2)Cl(3)](+) and [Au(3)(tripod|)(3)Cl](2+). The silver(I) complexes, 7 and 8 appear to contain linear and tetrahedral Ag(I), respectively.