The isoelectronic replacement of E = P+ and Si in the trinuclear organotin-oxo clusters [Ph2E(OSntBu2)2O•tBu2Sn(OH)2]

The trinuclear organotin-oxo cluster [Ph2P(OSntBu(2))(2)O.tBu(2)Sn(OH)(2)][O3SCF3] (6), was prepared in good yield by the consecutive reaction of (tBu(2)SnO)(3) with F3CSO3H and Ph2PO2H, and adopts a common tricyclic ESn3O3X2 structural motif with E = P; X = OH, similar to those found in the recently reported species [M(OSntBu(2))(2)O.tBu(2)Sn(OH)(2)] [M = Ph2Si (1), Me2Si (2), CO (3), MesB (4)] and [Ph2Si(OSntBu(2))(2)O.tBu(2)SnF(2)] (5) where E = Si, C, B and X OH, F. Compound 6 was characterized by multinuclear NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry and single-crystal X-ray diffraction analysis. A natural population analysis (NPA) performed on the B3LYP/LANL2DZ level of theory for the molecular structures of the isoelectronic species [Ph2Si(OSntBu(2))(2)O.tBu(2)Sn(OH)(2)] (1) and [Ph2P(OSntBu(2))(2)O.tBu(2)Sn(OH)(2)](+) (6a) suggests that the positive charge of the latter is partially delocalised over the phenyl rings. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.