Synthesis, spectroscopic properties and crystal structure of organophosphoryl polyoxotungstate alpha-[Bu_4N]_3H[PhCH_2P(O)]_2SiW_(11)O_(39)

摘要

Reaction of the monovacant heteropolyanions alpha-[SiW_(11)O_(39)]~(8-) with PhCH_2PO(OH)_2 leads to the formation of the organophosphoryl derivative alpha-[Bu_4N]_3H[PhCH_2P(O)]_2SiW_(11)O_(39) (1). Single-crystal X-ray diffraction analysis shows that the crystal is monoclinic with space group P2_1 and the unit cell parameters: a= 14.386 (3) A, 6 = 27.015 (5)A, c = 25.480 (5)A, alpha = 90 deg, beta = 91.44 (3) deg , gamma = 90 deg, V=9899 (3)A~3. Z = 4, D_c = 2.467 g cm~(-1), lambda (Mo-K alpha) = 0.071073 nm, R_1= 0.0638, wR_2 = 0.1364. The hybrid anion consists of an alpha-[SiW_(11)O_(39)]~(8-) framework on which two equivalent organophosphoryl groups are grafted through P-O-W bridges; each of the two PhCH_2P(O) groups are connected to two terminal oxygen atoms belonging to a triad and a diad, respectively.