Noninnocent dithiolene ligands: a new oxomolybdenum complex possessing a donor-acceptor dithiolene ligand.
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.
Matz
Kelly G
KG
Department of Chemistry, Bryn Mawr College, 101 North Merion Avenue, Bryn Mawr, Pennsylvania 19010-2899, USA.
Mtei
Regina P
RP
Leung
Belinda
B
Burgmayer
Sharon J Nieter
SJ
Kirk
Martin L
ML
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*
D008024:Ligands; D008667:Metalloproteins; D009942:Organometallic Compounds; D013871:Thiones; D008982:Molybdenum