期刊
ORGANOMETALLICS
卷 29, 期 8, 页码 1924-1933出版社
AMER CHEMICAL SOC
DOI: 10.1021/om900980a
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资金
- Ministry of Education (MOE) of Singapore [R-143-000-373-112]
- National University of Singapore
- KAUST
A series of N-heterocyclic carbene (NHC) complexes CpMo(CO)(2)(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, X = Br, 3; NHC = IBz = 1,3-dibenzylimidazol-2-ylidene, X = Br, 4a, and X = Cl, 4h; NHC = 1-methyl-3-propylimidazol-2-ylidene, X = Br, 5) and [CpMo(CO)(2)(IMes)(CH3CN)][BF4] (6) have been synthesized and fully characterized. The stability of metal-NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400 h(-1)) and selective olefin epoxidation catalyst. While under oxidative conditions (in the presence of TBHP), compounds 1-5 decompose into imidazolium bromide and imidazolium polyoxomolybdate. The formation of polyoxomolybdate as oxidation products had not been observed in a similar epoxidation catalyzed by Mo(II) and Mo(VI) complexes. DFT studies suggest that the presence of Br destabilizes the CpMo(VI) oxo NHC carbene species, consistent with the experimental observations.
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