Synthese und reaktivität kohlenwasserstoffüberbrückter komplexe von Mangan, Rhenium, Molybdän und Wolfram

Abstract

The hydrocarbon-bridged complexes M(CH 2) n M (M = Mn(CO) 5: n = 5 ( 2b), 10 ( 2c); M = Re(CO) 5: n = 5 ( 3b), 10 ( 3c); M = (η 5-C 5H 5)Mo(CO) 3: n = 5 ( 4b), 10 ( 4c); M = (η 5-C 5H 5)W(CO) 3: n = 10 ( 5c)) are obtained by reaction of the bistriflates Y(CH 2) n Y (Y = F 3CSO 3, n = 5 ( 1b), 10 ( 1c)) with the carbonyl metalates [M(CO) 5] − (M = Mn ( 2), Re ( 3)) and [(η 5-C 5H 5)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 SO 2 and CO, respectively, on the complexes 2a- c and 4b, c results in the formation of the sulfinato-S complexes [(η 5-C 5H 5)(OC) 3MoSO 2(CH 2) n O 2SMo(CO) 3(η 5-C 5 H 5)] ( n = 5 ( 4b′), 10 ( 4c′)) and the diacyl-bridged compounds [(OC) 5MnC (O)(CH 2) n (O)CMn(CO) 5] ( n = 3 ( 2a′), 10 ( 2c′)). According to an X-ray structural analysis, the monoacyl complex [(OC) 5MnC(O)(CH 2) 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-σ bond in 2b,c and 3b,c.