135944-68-2Relevant academic research and scientific papers
Synthesis and catalytic properties of heterobimetallic complexes of the tripod ligand HC(PPh2)3. X-ray molecular structures of [Rh(COD){HC(PPh2)3}Au(PPh3)](BF 4)2 and [RhCu2{HC(PPh2)3}2(THF) 2(CH3CN)2](BF4)2(F)
El-Amouri,Bahsoun,Fischer,Osborn,Youinou
, p. 3582 - 3588 (2008/10/08)
Treatment of [M(COD){HC(PPh2)3}]BF4 (M = Rh, Ir; 1a, 1b) with 1 equiv of the complex [Au-(PPh3)(THF)]BF4 in THF/CH2Cl2 at room temperature afforded the binuclear species [M(COD){HC-(PPh2)3}Au(PPh3)](BF 4)2 (M = Rh, Ir; 2a, 2b). The molecular structure of 2a showed both rhodium and gold bound to a single tripod ligand in a clamped arrangement with a rhodium to gold separation of 5.431 (1) ?. The reactions of molecular hydrogen and carbon monoxide with these complexes have been studied. When the mononuclear species [Rh(COD){HC(PPh2)3}]BF4 (1a) was treated with [Cu(CH3CN)4]BF4 in acetonitrile, the heterobinuclear complex [Rh(CH3CN)3Cu{HC(PPh2)3}](BF 4)2 (6) was obtained. 6 transforms in CH2Cl2/THF to give the trinuclear species [RhCu2{HC(PPh2)3}2(THF) 2(CH3CN)2](BF4)2(F) (7) for which an X-ray molecular structure was also determined. In the structure the rhodium lies on a center of symmetry, the two copper(I) ions each being 5.353 (4) ? distant from rhodium. The tetracoordinate planar arrangement of four phosphorus atoms about the rhodium results from the coordination of two tripod ligands, each providing two donor sites, leaving one phosphorus atom on each tripod to bind each Cu(I), which possesses a trigonal-planar coordination geometry. The catalytic properties of these new complexes for the hydrogenation of olefins have been briefly compared in order to probe the effect of the presence of the coinage metal on such processes. 2a·2H2O·Et2O crystallizes in the monoclinic space group P21/n (No. 14), a = 20.704 (5) ?, b = 13.686 (3) ?, c = 23.573 (5) ?, β = 109.42 (2)°, and Z = 4. The structure was refined to R = 6.4 and Rw = 10.7%, using 6924 reflections. 7·2C6H6 crystallizes in the triclinic space group P1 (No. 2), a = 13.544 (3) ?, b = 14.741 (3) ?, c = 13.156 (3) ?, α = 101.69 (2)°, β = 98.29 (2)°, γ = 62.76 (2)°, and Z = 1. The structure was refined to R = 10.1 and Rw = 13.6%, using 4437 reflections.
