Bi- and poly-metallic cyanide-bridged complexes of the redox-active cyanomanganese nitrosyl unit [Mn(CN)(PR3)(NO)(eta-C5H4Me)

Dalton Transactions : an International Journal of Inorganic Chemistry
Christopher J AdamsPhilip H Rieger

Abstract

Cationic nitrile complexes and neutral halide and cyanide complexes, with the general formula [MnL1L2(NO)(eta-C5H4Me)]z, undergo one-electron oxidation at a Pt electrode in CH2Cl2. Linear plots of oxidation potential, Eo', vs. nu(NO) or the Lever parameters, EL, for L1 and L2, allow Eo' to be estimated for unknown analogues. In the presence of TlPF6, [MnIL'(NO)(eta-C5H4Me)] reacts with [Mn(CN)L(NO)(eta-C5H4Me)] to give [(eta5-C5H4Me)(ON)LMn(mu-CN)MnL'(NO)(eta5-C5H4Me)][PF6] which undergoes two reversible one-electron oxidations; DeltaE, the difference between the potentials for the two processes, differs significantly for stable cyanide-bridged linkage isomers. Novel pentametallic complexes such as [Mn[(mu-NC)Mn(CNBut)(NO)(eta5-C5H4Me)]4(OEt2)][PF6]2 and [Mn[(mu-NC)Mn(CNXyl)(NO)(eta5-C5H4Me)]4(NO3-O,O')][PF6], containing a trigonal bipyramidal and a distorted octahedral Mn(II) centre, respectively, result either from slow decomposition of the binuclear cyanide-bridged species or from the reaction of anhydrous MnI2 with four equivalents of [Mn(CN)L(NO)(eta5-C5H4Me)] in the presence of TlPF6.

References

Mar 28, 1996·Chemical Reviews·Neil G. Connelly, William E. Geiger

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Citations

Mar 21, 2008·Chemical Communications : Chem Comm·W Michael Laidlaw, Robert G Denning
Aug 19, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher J AdamsSriwipha Onganusorn
Aug 19, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher J AdamsRowena L Paul
Apr 9, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher J AdamsSriwipha Onganusorn
Jul 21, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher J AdamsAndrew J Wood
May 31, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Christopher J AdamsA Guy Orpen

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