Abstract
The reaction of the tetranuclear iron complex [ $$\upmu _{4}$$ -Sulfido-bis{( $$\upmu $$ -2-furylmethanethiolato)bis[tricarbonyliron](Fe—Fe)}] 1 with $$\hbox {PPh}_{3}$$ was explored. The reaction leads to the formation of the mono-substituted complex [ $$\hbox {Fe}_{2}(\upmu $$ -2-furylmethanethiolate) $$_{2}(\hbox {CO})_{5}(\hbox {PPh}_{3})$$ ] 2. X-ray crystal structure has been reported for complex 2. Complexes 1 and 2 were found to be active catalysts for proton reduction. Complexes 1 and 2 showed comparable catalytic activity for proton reduction to dihydrogen. SYNOPSIS Monothiolate-bridged, all carbonyl tetranuclear iron complex [ $$\upmu _{4}$$ -Sulfido-bis{( $$\upmu $$ -2-furylmethanethiolato)bis[tricarbonyliron](Fe—Fe)}] 1 and phosphine-substituted diiron complex [ $$\hbox {Fe}_{2}(\upmu $$ -furylmethanethiolate) $$_{2}(\hbox {CO})_{5}(\hbox {PPh}_{3})$$ ] 2 have been investigated for electrocatalytic proton reduction.
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