Metal-sulfur dπ-pπ buffering of the oxidations of metal-thiolate complexes:: Photoelectron spectroscopy of (η5-C5H5)Fe(CO)2SR (SR = SCH3, StBu) and (η5-C5H5)Re(NO)(PR3)SCH3 (PR3 = PiPr3, PPh3)

The metal-sulfur bonding present in the transition metal-thiolate complexes CpFe(CO)(2)SCH3, CpFe(CO)(2)(SBu)-Bu-t, CpRe(NO)((PPr3)-Pr-i)SCH3, and CpRe(NO)(PPh3)SCH3 (Cp = eta(5)-C5H5) is investigated via gas-phase valence photoelectron spectroscopy. For all four complexes a strong d pi-p pi interaction exists between a filled predominantly metal d orbital of the [CpML2](+) fragment and the purely sulfur 3p pi lone pair of the thiolate. This interaction results in the highest occupied molecular orbital having substantial M-S pi* antibonding character. In the case of CpFe(CO)(2)SCH3, the first (lowest energy) ionization is from the Fe-S pi* orbital, the next two ionizations are from predominantly metal d orbitals, and the fourth ionization is from the Fe-S pi orbital. The pure sulfur p pi lone pair of the thiolate fragment is less stable than the filled metal d orbitals of the [CpFe(CO)(2)](+) fragment, resulting in a Fe-S pi* combination that is higher in sulfur character than the Fe-S pi combination. Interestingly, substitution of a tert-butyl group for the methyl group on the thiolate causes little shift in the first ionization, in contrast to the shift observed for related thiols. This is a consequence of the delocalization and electronic buffering provided by the Fe-S d pi-p pi interaction. For CpRe(NO)((PPr3)-Pr-i)SCH3 and CpRe(NO)(PPh3)SCH3, the strong acceptor ability of the nitrosyl ligand rotates the metal orbitals for optimum backbonding to the nitrosyl, and the thiolate rotates along with these orbitals to a different preferred orientation from that of the Fe complexes. The initial ionization is again the M-S pi* combination with mostly sulfur character, but now has considerable mixing among several of the valence orbitals. Because of the high sulfur character in the HOMO, ligand substitution on the metal also has a small effect on the ionization energy in comparison to the shifts observed for similar substitutions in other molecules. These experiments show that, contrary to the traditional interpretation of oxidation of metal complexes, removal of an electron from these metal-thiolate complexes is not well represented by an increase in the formal oxidation state of the metal, nor by simple oxidation of the sulfur, but instead is a variable mix of metal and sulfur content in the highest occupied orbital. (C) 2007 Elsevier B.V. All rights reserved.