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The synthesis and redox properties are presented for the electron-rich bis(monothiolate)s Fe 2 (SR) 2 (CO) 2 (dppv) 2 for R = Me ([1] 0 ), Ph ([2] 0 ), CH 2 Ph ([3] 0 ). Whereas related derivatives adopt C 2 -symmetric Fe 2 (CO) 2 P 4 cores, [1] 0 -[3] 0 have C s symmetry resulting from the unsymmetrical steric properties of the axial vs equatorial R groups. Complexes [1] 0 -[3] 0 undergo 1e - oxidation upon treatment with ferrocenium salts to give the mixed valence cations [Fe 2 (SR) 2 (CO) 2 (dppv) 2 ] + . As established crystallographically, [3] + adopts a rotated structure, characteristic of related mixed valence diiron complexes. Unlike [1] + and [2] + and many other [Fe 2 (SR) 2 L 6 ] + derivatives, [3] + undergoes C-S bond homolysis, affording the diferrous sulfido-thiolate [Fe 2 (SCH 2 Ph)(S)(CO) 2 (dppv) 2 ] + ([4] + ). According to X-ray crystallography, the first coordination spheres of [3] + and [4] + are similar, but the Fe-sulfido bonds are short in [4] + . The conversion of [3] + to [4] + follows first-order kinetics, with k = 2.3 × 10 -6 s -1 (30 °C). When the conversion is conducted in THF, the organic products are toluene and dibenzyl. In the presence of TEMPO, the conversion of [3] + to [4] + is accelerated about 10×, the main organic product being TEMPO-CH 2 Ph. DFT calculations predict that the homolysis of a C-S bond is exergonic for [Fe 2 (SCH 2 Ph) 2 (CO) 2 (PR 3 ) 4 ] + but endergonic for the neutral complex as well as less substituted cations. The unsaturated character of [4] + is indicated by its double carbonylation to give [Fe 2 (SCH 2 Ph)(S)(CO) 4 (dppv) 2 ] + ([5] + ), which adopts a bioctahedral structure.

Electron-Rich, Diiron Bis(monothiolato) Carbonyls: C–S Bond Homolysis in a Mixed Valence Diiron Dithiolate