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Chromium and ruthenium complexes of the chelating phosphine borane H3B·dppm are reported. Addition of H3B·dppm to [Cr(CO)4(nbd)]
(nbd = norbornadiene) affords [Cr(CO)4(η1-H3B·dppm)] in which the borane is linked to the metal through a single B–H–Cr interaction. Addition of H3B·dppm to [CpRu(PR3)(NCMe)2]+
η5-C5H5) results in [CpRu(PR3)(η1-H3B·dppm)][PF6]
(R = Me, OMe) which also show a single B–H–Ru interaction. Reaction with [CpRu(NCMe)3]+ only resulted in a mixture of products. In contrast, with [Cp*Ru(NCMe)3]+
η5-C5Me5) a single product is isolated in high yield: [Cp*Ru(η2-H3B·dppm)][PF6]. This complex shows two B–H–Ru interactions. Reaction with L = PMe3 or CO breaks one of these and the complexes [Cp*Ru(L)(η1-H3B·dppm)][PF6] are formed in good yield. With L = MeCN an equilibrium is established between [Cp*Ru(η2-H3B·dppm)][PF6] and the acetonitrile adduct. [Cp*Ru(η2-H3B·dppm)][PF6] can be considered as being “operationally unsaturated”, effectively acting as a source of 16-electron [Cp*Ru(η1-H3B·dppm)][PF6]. All the new compounds (apart from the CO and MeCN adducts) have been characterised by X-ray crystallography. The solid-state structure of H3B·dppm is also reported.
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