TY - JOUR

T1 - The solid-state, solution and gas–phase interactions of diphosphane monooxide spacers with heavier group 8,9 transition metals and gallium in novel organometallic assemblies: An experimental and computational study.

AU - Monakhov, Kirill Yu.

AU - Grachova, Elena V.

AU - Starova, Galina L.

AU - Zessin, Thomas

AU - Linti, Gerald

PY - 2012

Y1 - 2012

N2 - New mono-substituted carbonyl clusters [M3(CO)11(DPMO)] (M = Os, Ru; 1–4) and [Rh6(CO)15(DPMO)] (5, 6) were obtained from the reactions of non-symmetrical bifunctional diphosphane monoxides (DPMOs, Ph2P(CH2)nP(O)Ph2, n = 2, 3) with triangular clusters [Os3(CO)12] and [Ru3(CO)12], and octahedral cluster [Rh6(CO)15(NCMe)] under mild conditions. The electrophilic addition of GaCl3 to 1–6 in toluene results in coordination-based molecular assemblies [M3(CO)11(DPMO)(GaCl3)] (M = Ru, Os; 7–10) and [Rh6(CO)15(DPMO)(GaCl3)] (11, 12). 1–12 were characterised by 31P{1H} NMR, IR spectroscopy, and FAB mass spectrometry. The crystal structures of 1, 2 and 7 were determined by single-crystal X-ray analysis. 7 is the first solid-state characterised osmium-gallium bridging complex. The latter and its precursor 1 were studied by density functional calculations in the gas phase and in solution in order to better understand their structures and properties. The nature of the binding interactions between the constitutive units of

AB - New mono-substituted carbonyl clusters [M3(CO)11(DPMO)] (M = Os, Ru; 1–4) and [Rh6(CO)15(DPMO)] (5, 6) were obtained from the reactions of non-symmetrical bifunctional diphosphane monoxides (DPMOs, Ph2P(CH2)nP(O)Ph2, n = 2, 3) with triangular clusters [Os3(CO)12] and [Ru3(CO)12], and octahedral cluster [Rh6(CO)15(NCMe)] under mild conditions. The electrophilic addition of GaCl3 to 1–6 in toluene results in coordination-based molecular assemblies [M3(CO)11(DPMO)(GaCl3)] (M = Ru, Os; 7–10) and [Rh6(CO)15(DPMO)(GaCl3)] (11, 12). 1–12 were characterised by 31P{1H} NMR, IR spectroscopy, and FAB mass spectrometry. The crystal structures of 1, 2 and 7 were determined by single-crystal X-ray analysis. 7 is the first solid-state characterised osmium-gallium bridging complex. The latter and its precursor 1 were studied by density functional calculations in the gas phase and in solution in order to better understand their structures and properties. The nature of the binding interactions between the constitutive units of

KW - Transition metals / Gallium / Linker / Crystal Structures / Density functional calculations

U2 - 10.1016/j.jorganchem.2012.03.003

DO - 10.1016/j.jorganchem.2012.03.003

M3 - статья

VL - 714

SP - 22

EP - 31

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1

ER -