Synthesis and redox reactivity of a series of Fe2(µ-S) complexes

Abstract

Reaction of (PhBP_3)FeCl (PhBP_3 = [PhB(CH_2PPh_2)_3]-) with [NBu_4][SH] and a base yields the dimeric bridging sulfide species [(PhBP_3)Fe]_2(μ-S). Cyclic voltammetry reveals two reversible redn. events spanning three distinct oxidn. states from Fe(II)/Fe(II) to Fe(I)/Fe(I). The mixed valent {[(PhBP_3)Fe]_2(μ-S)}- and the dianionic {[(PhBP_3)Fe]_2(μ-S)}^2- species have been isolated via chem. redn. and structurally characterized. Addnl. reactivity of these complexes has been investigated, including the reaction of [(PhBP_3)Fe]_2(μ-S) with CO to yield [(PhBP_3)FeCO]_2 (μ-S). This complex also shows a reversible redn. and evidence of reductive electrocatalytic activity under acidic conditions has been obsd.

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