Tetrahedral chlorometal derivatives of redox-active cyanomanganese ligands: synthesis, structures and solvatochromic properties of a new class of cyanide-bridged complexes

Abstract

First row transition metal (M = Mn–Ni) dichlorides react with cyanomanganese(I) carbonyl ligands to give novel paramagnetic bi- and poly-nuclear cyanide-bridged complexes, X-ray structural studies on which are consistent with Fe^IIIMn^I, Fe^IIIMn^II and Mn^IIMn^II core oxidation states for [Cl₃M(µ-NC)Mn(CO)(dppm)₂]^z (M = Fe, z = 0, 1; M = Mn, z = 0) respectively; Fe^IIIMn^I complexes show strong solvatochromism, consistent with low spin d⁶ octahedral Mn^I to tetrahedral d⁵ Fe^III charge transfer.