Oxidative addition of phosphine-tethered thiols to iron carbonyl: binuclear phosphinothiolate complexes, (mu-SCH(2)CH(2)PPh(2))(2)Fe(2)(CO)(4), and hydride derivatives.

The mononuclear complex Fe(CO)(4)(PPh(2)CH(2)CH(2)SH), 1, is isolated as an intermediate in the overall reaction of PPh(2)CH(2)CH(2)SH with [Fe(0)(CO)(4)] sources to produce binuclear bridging thiolate complexes. Photolysis is required for loss of CO and subsequent S-H activation to generate the metal-metal bonded Fe(I)-Fe(I) complex, (mu-SCH(2)CH(2)PPh(2))(2)Fe(2)(CO)(4), 2. Isomeric forms of 2 derive from the apical or basal position of the P-donor ligand in the pseudo square pyramidal S(2)Fe(CO)(2)P coordination spheres. This position in turn is dictated by the stereochemistry of the mu-S-CH(2) bond, designated as syn or anti with respect to the Fe(2)S(2) butterfly core. Addition of strong acids engages the Fe(I)-Fe(I) bond density as a bridging hydride, [(mu-H)-anti-2](+)[SO(3)CF(3)](-) or [(mu-H)-syn-2](+)[SO(3)CF(3)](-), with formal oxidation to Fe(II)-H-Fe(II). Molecular structures of anti-2, syn-2, and [(mu-H)-anti-2](+)[SO(3)CF(3)](-) were determined by X-ray crystallography and show insignificant differences in distance and angle metric parameters, including the Fe-Fe bond distances which average 2.6 A. The lack of coordination sphere rearrangements is consistent with the ease with which deprotonation occurs, even with the weak base, chloride. The Fe(I)-Fe(I) bond, supported by bridging thiolates, therefore presents a site where a proton might be taken up and stored as a hydride without impacting the overall structure of the binuclear complex.