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DOI: 10.1039/A902478F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3185-3190

Triphenylboron adducts of redox-active cyanomanganese ligands[hair space]†

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Dena Bellamy, Neil G. Connelly, Owen M. Hicks and A. Guy Orpen

Abstract

The reaction of [Mn(CN)(PR3)(NO)(η-C5H4Me)] (R = Ph or OPh) with [AuCl(tht)] (tht = tetrahydrothiophene) in the presence of Na[BPh4] gave [Mn(CNBPh3)(PR3)(NO)(η-C5H4Me)], X-ray studies on which (R = OPh) confirm addition of triphenylboron to the nitrogen atom of the cyanomanganese centre. Comparison of the geometry of the Ph3B–NC interaction, as measured by the mean C–B–C angle and mean B–C length, with those of L·BPh3 species in the Cambridge Structural Database showed the manganese ligand to be a relatively weak donor comparable with a range of other N and O ligands. The complexes [Mn(CNBPh3)(PR3)(NO)(η-C5H4Me)], as well as cis-[Mn(CNBPh3)(CO)2{P(OEt)3}(dppm)] and trans-[Mn(CNBPh3)(CO)(dppm)2], can be prepared directly from BPh3 and the appropriate cyanomanganese ligand. Each of the complexes undergoes one-electron oxidation at a platinum disc electrode in CH2Cl2 and the reaction of trans-[Mn(CNBPh3)(CO)(dppm)2] with [Fe(η-C5H5)2][PF6] gives trans-[Mn(CNBPh3)(CO)(dppm)2][PF6].

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