Unexpected Reaction of Fe3(CO)12 with Dialkyldithiophosphate: The Case of P–S Bond Activation

Abstract

The reaction of Fe3(CO)12 with O,O′‐dialkyldithiophosphate diethylamine salts (RO)2P{S}SH·Et2NH (R = CH3, CH2CH3) resulted in the formation of trinuclear cluster complex {μ‐SP(OR)2Fe[S2P(OR)2)]S‐μ]}Fe2(CO)6 [R = CH3 (1), CH2CH3 (2)]. The two complexes were characterized by elemental analysis, FT‐IR, NMR (1H, 31P and 13C) spectroscopy, as well as by X‐ray diffraction analyses. Crystal structures reveal that one P–S bond is cleaved during the reaction, yielding the [2Fe2S] unit together with FePS3(CO)2. The other dialkyldithiophosphate coordinated with iron by S, S chelating model. The trinuclear cluster was observed with the P‐Fe and S–Fe bond formed by the P‐S activation. In addition, the electrochemical properties for complex 2 as an illustration was also studied by cyclic voltammetry in MeCN.