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Pure Appl. Chem., 2003, Vol. 75, No. 9, pp. 1165-1173

Reactions of boranes and metallaboranes with phosphines

Lawrence Barton, Oleg Volkov, Mitsuhiro Hata, Paul McQuade and Nigam P. Rath

Department of Chemistry and Biochemistry and the Center for Molecular Electronics, University of Missouri-St.Louis, St.Louis, MO 63121, USA

Abstract: This paper reports extensions of the well-established field of phosphine–borane chemistry. Linked clusters, for example, {[(PPh3)2(CO)OsB4H7-3-BH2-PPh2]2 [(Fe(C5H4)2]}, are formed in reactions of rigid backboned bidentate phosphines with {2,2,2-(PPh3)2(CO)-nido-2-OsB5H9]. Reaction of bidentate phosphines with the unsaturated clusters [8,8-PPh3)2-nido-8,7-RhSB9H10] and [9,9-(PPh3)2-nido-9,7,8-RhC2B8 H11] leads to the isolation of novel species such as {1-(PPh3)[1,3-(µ-dppm)]-closo -1,2-RhSB9H8},with a dppm molecule bridging adjacent metal and boron vertices in the cage, [1,1-(ç2-dppe)-3-(ç1-dppm)-closo-1,2-RhSB 9H8], a mixed ligand system, and {9,9-ç2-[(ç2-BH3)PPh2PCH2 PPh2]-nido- 9,7,8-RhC2B8H11} which contains a bidentate dppm BH3 moiety. The formation of bidentate phosphine-linked main group transition-metal moieties such as [BH3PPh2(CH)nPPh2IrCp*Cl2] is also described as is an example of a bidentate phosphine-polyhedral borane adduct [NR4][B11H12(dppm)] in which the borane cage is isoelectronic with [B11H14]. Finally, a novel oxidative coupling reaction promoted by Cp2ZrCl2/n-BuLi to form the new nonaborane cage system, arachno -B9H11(PPh3)2, an unusual homolog of the well-known species B10H12(PPh3)2, is reported.