Coordination chemistry of a bulky redox-active cyanomanganese carbonyl ligand: N-bound tetrahedral complexes of 3d metals
- 1 January 2000
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 1637-1643
- https://doi.org/10.1039/b001782p
Abstract
The sterically hindered redox-active cyanomanganese carbonyl complex trans-[Mn(CN)(CO)(dppm)2] acts as an N-donor ligand towards MCl2 (M = Mn, Co or Ni) to give the cyanide-bridged tetrahedral (at M) complexes [Cl2(thf)M(μ-NC)MnLx] {Lx = (CO)(dppm)2}. Displacement of the labile thf ligand by chloride ion affords anionic [Cl3M(μ-NC)MnLx]− which is oxidised to [Cl3M(μ-NC)MnLx], containing two paramagnetic centres, tetrahedral M(II) and low spin octahedral Mn(II). The cobalt(II) complex [Cl2(thf)Co(μ-NC)MnLx] also undergoes thf substitution with neutral N-donor ligands to give [Cl2L′Co(μ-NC)MnLx] {L′ = 4,4′-bipy or (NC)Mn(PPh3)(NO)(η-C5H4Me)}; the latter is oxidised to the mixed valence trimetallic cation [Cl2CoII{(μ-NC)MnIILx}{(μ-NC)MnI(PPh3)(NO)(η-C5H4Me)}]+. X-Ray structural studies on [Cl2(thf)M(μ-NC)MnLx] (M = Co, Mn or Ni) and [Cl3Mn(μ-NC)MnLx] show distortion of the M–N–C angle to accommodate non-bonded interactions between the phenyl groups of the bulky Mn(dppm)2 moiety and the ligands at the tetrahedral metal; distortions of the tetrahedral valence angles at the MII centres of [Cl2(thf)M(μ-NC)MnLx] may in part be related to the weak binding of thf.Keywords
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