title: Noninnocent dithiolene ligands: a new oxomolybdenum complex possessing a donor-acceptor dithiolene ligand.
abstract: A new monoanionic dithiolene ligand is found in Tp*MoO(S(2)BMOQO). A combination of X-ray crystallography, electronic absorption spectroscopy, resonance Raman spectroscopy, and bonding calculations reveal that the monoanionic dithiolene ligand possesses considerable thiolate-thione character resulting from an admixture of an intraligand charge transfer excited state into the ground state wave function. The unusual dithiolene exhibits a highly versatile donor-acceptor character that dramatically affects the Mo(IV/V) redox couple and points to a potentially noninnocent role of the pterin fragment in pyranopterin Mo enzymes.
authors.affiliation: Department of Chemistry, Bryn Mawr College, 101 North Merion Avenue, Bryn Mawr, Pennsylvania 19010-2899, USA.
authors.forename: Kelly G
authors.initials: KG
authors.lastname: Matz
authors.forename: Regina P
authors.initials: RP
authors.lastname: Mtei
authors.forename: Belinda
authors.initials: B
authors.lastname: Leung
authors.forename: Sharon J Nieter
authors.initials: SJ
authors.lastname: Burgmayer
authors.forename: Martin L
authors.initials: ML
authors.lastname: Kirk
mesh_terms: D000042:Absorption; D004579:Electron Transport; D008024:Ligands; D008667:Metalloproteins / Q000737:chemistry / Q000378:metabolism; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013057:Spectrum Analysis; D013871:Thiones / Q000737:chemistry*
chemical_list: D008024:Ligands; D008667:Metalloproteins; D009942:Organometallic Compounds; D013871:Thiones; D008982:Molybdenum