Novel binary compounds of group 15 elements: Synthesis and characterisation of [Sb-4(PSiMe(2)Thex)4], [Sb-4(AsSiiPr(3))(4)] and [Sb-2(PSiPh(2)tBU)4]

摘要

The low-temperature reactions of Me(2)ThexSiPLi(2) (Thex = CMe(2)iPr) and iPr(3)SiAsLi(2) with SbCl3 in a 3:2 molar ratio yields the cage compounds [Sb-4(PSiMe(2)Thex)(4)] (1) and [Sb-4(AsSiiPr(3))(4)] (2), respectively. The metal salt SbBr3 reacts with tBuPh(2)SiPLi(2) at -70degreesC to give the bicyclic compound [Sb-2(PSiPh(2)tBu)(4)] (3). Compounds 1-3 were characterised by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single-crystal X-ray diffraction. The structures of 1 and 2 reveal that the both compounds adopt a structure similar to those of realgar (As4S4). The central structural motif is an Sb4Y4 cage (Y = P, As), consisting of four five-membered rings with common edges. The bicyclic compound 3 is composed of five-membered and three-membered rings sharing a common Sb-2 bridgehead. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)