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Metallaboratranes:  Tris(methimazolyl)borane Complexes of Rhodium(I)

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posted on 02.01.2006, 00:00 by Ian R. Crossley, Anthony F. Hill, Anthony C. Willis
The syntheses and reactivity of the first rhodaboratranes, [RhX(PPh3){B(mt)3}] (X = Cl, H) and [Rh(η4-C8H12){B(mt)3}]Cl, are described in detail together with preliminary investigations of the mechanistic processes involved. The subsequent exploitation and circumvention of the lability of [RhCl(PPh3){B(mt)3}] in the synthesis of a range of isonitrile, [Rh(CNR)(PPh3){B(mt)3}]Cl (R = tBu, C6H3Me2-2,6, C6H2Me3-2,4,6), phosphine, [Rh(PMe3)n(PPh3)2-n{B(mt)3}]Cl (n = 0, 1, 2), and dialkyldithiocarbamate, [Rh(S2NEt2){B(mt)3}]Cl, complexes is described, along with the attempted synthesis of [Rh(CNtBu)2{B(mt)3}]Cl from [Rh(η4-C8H12){B(mt)3}]Cl. Single-crystal X-ray structure determinations of [Rh(L)(L‘){B(mt)3}]Cl (L = CNtBu, CN(C6H3Me2-2,6), L‘ = PPh3; L = L‘ = PMe3) are reported.