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Neutral and cationic mono- and bis-N-heterocyclic carbene complexes derived from manganese and rhenium carbonyl precursors


Reference:

Martin, T. A., Ellul, C. E., Mahon, M. F., Warren, M. E., Allan, D. and Whittlesey, M. K., 2011. Neutral and cationic mono- and bis-N-heterocyclic carbene complexes derived from manganese and rhenium carbonyl precursors. Organometallics, 30 (8), pp. 2200-2211.

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Official URL:

http://dx.doi.org/10.1021/om1011853

Abstract

Synthesis of the manganese and rhenium bis-NHC complexes fac-M((IPr2Me2)-Pr-i)(2)(CO)(3)X ((IPr2Me2)-Pr-i = 1,3-diisopropyl-4-5-dimethylimidazol-2-ylidene; M = Mn, X = Br, 1; M = Re, X = Cl, 2) is achieved by treatment of M(CO)(5)X with 2 equiv of the free carbene. Halide abstraction by NaBAr4F (BAr4F = B{C6H5(3,5-CF3)(2)}(4)) yields the spectroscopically characterized agostic species [M((IPr2Me2)-Pr-i)(2)(CO)(3)]BAr4F (M = Mn, 3; M = Re, 4). These react rapidly with CO to form the tetracarbonyi compounds cis-[M((IPr2Me2)-Pr-i)(2)(CO)(4)]BAr4F (M = Mn, 5; M = Re, 6). Addition of 1 equiv of IPr (1,3-bis(2,6-diisopropylphenypimidazol-2-ylidene) to M(CO)(5)X yields the moriocarbene complexes M(IPr(CO)(4)X (M = Mn, 8; M = Re, 9), which, in the case of Re, affords the dichloromethane complex [Re(IPr)(CO)(4)(CH2Cl2)]BAr4F (11) upon reaction with AgOTf/NaBAr4F. Removal of halide from 8 and 9 by AgOTf/NaBAr4F in the presence of CO affords the cationic pentacarbonyl species [M(IPr)(CO)(5)]BAr4F (M = Mn, 13; M = Re, 14). Complexes 1, 2, 5, 6, 8, 9, 11, 13, and 14 have all been structurally characterized.

Details

Item Type Articles
CreatorsMartin, T. A., Ellul, C. E., Mahon, M. F., Warren, M. E., Allan, D. and Whittlesey, M. K.
DOI10.1021/om1011853
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code23676

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