Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions
KAUST DepartmentBiological and Environmental Sciences and Engineering (BESE) Division
KAUST Catalysis Center (KCC)
Chemical Science Program
Physical Sciences and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/561467
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AbstractA 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, 4b; NHC = 1-methyl-3-propylimidazol-2- ylidene, X = Br, 5) and [CpMo(CO)2(IMes)(CH3CN)][BF 4] (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 [CpMoO 2(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. © 2010 American Chemical Society.
SponsorsWe are grateful to the Ministry of Education (MOE) of Singapore Academic Research Fund (AcRF) Tier 1 Grant (WBS No. R-143-000-373-112). S.Y. L. also thanks National University of Singapore for the scholarship. K.W.H. acknowledges the support from KAUST baseline funding. We thank Ms. Geok Kheng Tan and Dr. Lip Lin Koh for determining the X-ray crystal structures.
PublisherAmerican Chemical Society (ACS)