Synthesis of Unsupported d1–dx Oxido-Bridged Heterobimetallic Complexes Containing VIV: A New Direction for Metal-to-Metal Charge Transfer
作者： Xinyuan Wu , Tao Huang , Travis T. Lekich , Roger D. Sommer , Walter W. Weare
DOI: 10.1021/ACS.INORGCHEM.5B00370
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摘要: Heterobimetallic complexes composed only of first-row transition metals [(TMTAA)VIV═O→MIIPy5Me2](OTf)2 (TMTAA = 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine; Py5Me2 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine; M MnII, FeII, CoII, NiII, CuII; OTf trifluoromethanesulfonate) have been synthesized through a dative interaction between terminal oxido and MII metal centers. This is the first series VIV═O→MII heterobimetallic containing an unsupported bridge. Among these five complexes, VIV═O→FeII (3b) has clear new absorption band upon formation dinuclear species (502 nm, e 1700 M–1 cm–1). feature assigned to metal-to-metal charge transfer (MMCT) from VIV which forms VV—O—FeI excited state. assignment supported by electrochemical data, electronic profiles, resonance Raman spectroscopy represents report visible-light induced MMCT in oxido-bridged mo...
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