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

Synthesis of the manganese and rhenium bis-NHC complexes fac-M(IiPr2Me2)2(CO)3X (IiPr2Me2 = 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)5X with 2 equiv of the free carbene. Halide abstraction by NaBAr4F (BAr4F = B{C6H3(3,5-CF3)2}4) yields the spectroscopically characterized agostic species [M(IiPr2Me2)2(CO)3]BAr4F (M = Mn, 3; M = Re, 4). These react rapidly with CO to form the tetracarbonyl compounds cis-[M(IiPr2Me2)2(CO)4]BAr4F (M = Mn, 5; M = Re, 6). Addition of 1 equiv of IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to M(CO)5X yields the monocarbene complexes M(IPr)(CO)4X (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...