Unexpected Reaction of Fe 3 (CO) 12 with Dialkyldithiophosphate: The Case of P–S Bond Activation

The reaction of Fe 3 (CO) 12 with O,O ′‐dialkyldithiophosphate diethylamine salts (RO) 2 P{S}SH · Et 2 NH (R = CH 3 , CH 2 CH 3 ) resulted in the formation of trinuclear cluster complex {μ‐SP(OR) 2 Fe[S 2 P(OR) 2 )]S‐μ]}Fe 2 (CO) 6 [R = CH 3 ( 1 ), CH 2 CH 3 ( 2 )]. The two complexes were characterized by elemental analysis, FT‐IR, NMR ( 1 H, 31 P and 13 C) 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 FePS 3 (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.