Abstract
A series of manganese(II) arylphosphine complexes, [{Mn[P(aryl)3]X2}n][aryl = Ph, 4-ClC6H4, 4-MeC6H4, 4-MeOC6H4 or 2,4,6-(MeO)3C6H2; X = Cl, Br, I or NCS], have been synthesised and characterised. At ambient temperature all the complexes are inactive towards dioxygen binding, but at 228 K a toluene solution of [Mn{P(C6H4OMe-4)3}I2] absorbs 1 mol of O2 per mol of complex; this represents the first triarylphosphine manganese(II) complex to bind dioxygen. Cyclic voltammetric studies on these compounds suggest a one-electron transfer process which becomes more reversible as the temperature is lowered, thus indicating an electrochemical–chemical mechanism, with E°′ values influenced by both the anion and phosphine ligands.
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