TRIORGANOANTIMONY(V) DIORGANOPHOSPHINATES - CRYSTAL AND MOLECULAR STRUCTURE OF (DIPHENYLPHOSPHINATO)(HYDROXO)TRIMETHYLANTIMONY(V), EXHIBITING A POLYMERIC CHAIN SUPRAMOLECULAR SELF-ASSEMBLY THROUGH HYDROGEN BONDS

摘要

The reaction between R3SbCl2 (R = Me, Ph) and R'2PO2Na (R' = Me, Ph) afforded R3Sb(O2PR'(2))(2) derivatives, which were investigated by IR and multinuclear (H-1, C-13, P-31) NMR spectroscopy. Attempts to grow crystals of Me3Sb(O2PPh2)(2) led to colorless needles identified by X-ray diffractometry as Me3Sb(OH) [O(O)PPh2], produced by partial hydrolysis. Coordination around the central metal atom is distorted trigonal bipyramidal with carbon atoms of the SbMe3 unit in equatorial positions and two oxygen atoms occupying the axial positions [O--Sb--O 175.7(1)degrees]. The two antimony-oxygen distances are significantly different [Sb--O(H) 1.967(3) Angstrom, Sb--O(P) 2.235(2) Angstrom], as are the phosphorus-oxygen bond lengths in the basically monodentate diphenylphosphinato ligand [P double bond O 1.528(3) Angstrom, P double bond O 1.490(3) Angstrom]. The molecules are associated into polymeric chains through intermolecular hydrogen bonds between hydrogen of the hydroxo group and oxygen double bonded to phosphorus. (C) 1997 Elsevier Science Ltd. [References: 30]