Selective formation of bis(diphenylphosphino)-methanido- or -phosphido-bridged dihydridoruthenium-rhodium complexes in reactions of RuRhH2Cl(C8H12)(Ph2PCH2PPh2)2 with trialkylborohydrides as a function of solvent and reagent basicity |
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| Authors: | Hassan Benlaarab Bruno Chaudret Franoise Dahan Ren Poilblanc |
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| Institution: | Laboratoire de Chimie de Coordination du CNRS, Unité No. 8241 liée par convention à l'Université Paul Sabatier, 205 route de Narbonne, 31077 Toulouse Cedex France |
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| Abstract: | RuRhH2Cl(COD)(dppm)2 (1) (COD = 1,5-C8H12, DPPM = Ph2PCH2PPh2) does not react with LiBHEt3 in THF, but in toluene RuRhH2(PhPCH2PPh2)(dppm)(COD) (3) is formed quantitatively. In contrast, the reaction of 1 with KBH(sec-Bu)3 in THF selectively gives RuRhH2(CH(PPh2)2)(dppm)(COD) (4), whereas in toluene a mixture of 3 and 4 is obtained. Mechanisms are proposed for these reactions. The X-ray crystal structure of 4 · PhCH3 reveals direct coordination of a methanido group to rhodium and a long metal-metal distance (3.3006(6) Å). |
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