Synthese und Reaktivitaet kohlenwasserstoffueberbrueckter Komplexe von Mangan, Rhenium, Molybdaen und Wolfram

Article abstract of DOI:10.1016/0022-328X(92)83464-S

The hydrocarbon-bridged complexes M(CH2)nM (M=MN(CO)5: n=5 (2b), 10 (2c); M=Re(CO)5: n=5 (3b), 10 (3c); M=(η⁵-C5H5)Mo(CO)3: n=5 (4b), 10 (4c); M=(η⁵-C5H5)W(CO)3: n=10 (5c)) are obtained by reaction of the bistriflates Y(CH2)nY (Y=F3CSO3, n=5 (1b), 10 (1c)) with the carbonyl metalates ^- (M=Mn (2), Re (3)) and <(η⁵-C5H5)M(CO)3>^- (M=Mo (4), W (5)) in diethyl ether and THF, respectively.Depending on the solvent, the reaction of 1b with 2 also affords the cyclic carbene complex 2d.The action of SO2 and CO, respectively, on the complexes 2a-c and 4b,c results in the formation of the sulfinato-S complexes <(η⁵-C5H5)(OC)3MoSO2(CH2)nO2SMo(CO)3(η⁵-C5H5)> (n=5 (4b'), 10 (4c')) and the diacyl-bridged compounds <(OC)5MnC(O)(CH2)n(O)CMn(CO)5> (n=3 (2a'), 10 (2c')).According to an X-ray structural analysis, the monoacyl complex <(OC)5MnC(O)(CH2)3Mn(CO)5> (2e) crystallizes in the orthorhombic space group Cmca with Z=4, the acyl function being disordered. 1H NMR spectroscopic investigations indicate a hindered rotation about the C_α-C_β-? bond in 2b, c and 3b, c.