Zweikernige Mangan- und Rheniumkomplexe mit gemischt aliphatischen-aromatischen Kohlenwasserstoffbrücken / Dinuclear Manganese and Rhenium Complexes with Mixed Aliphatic-Aromatic Hydrocarbon Bridges

Abstract

The symmetrically hydrocarbon-bridged complexes (OC)5M-(CH2)n+1-X-(CH2)n+l-M(CO)5 [n = 1, X = 1,4-C6H4, M = Mn (2a), M = Re (3a); n = 2, X = 1,4-C6H4, M = Mn (2b), M = Re (3b); n = 1, X = 1,3-C6H4, M = Mn (5a), M = Re (6a); n = 2, X = 1,3-C6H4, M = Mn (5b), M = Re (6b); n = 1, X = 1,2-C6H4, M = Mn (8a), M = Re (9a); n = 2, X = 1,2-C6H4, M = Mn (8b), M = Re (9b)] are obtained by the reaction of the bistriflates X[(CH2)„-CH2-OSO2CF3]2 [X = 1,4-C6H4, n = 1 (la), n = 2 (lb); X = 1,3-C6H4, n = 1 (4a), n = 2 (4b); X = 1,2-C6H4, n = 1 (7a), n = 2 (7b)] with the carbonyl metalates [M(CO)5]- (M = Mn, Re) in THF and dimethyl ether, respectively. According to an X-ray structural analysis 8a crystallizes in the triclinic space group P1̅ with Ζ = 2. Depending on the solvent, the reaction of 7 a with [Mn(CO)5]~ affords also the cyclic carbene complex 10a. The behavior of the manganese compounds toward CO has been investigated exemplarily in the case of 8a and leads to the diacyl complex 1,2-C6H4[CH2CH2C(O)Mn(CO)5]2 (11). Upon reaction with Na2CO3/CH3OH 11 is converted to give the corresponding diester 1,2-C6H4[CH2CH2C(O)OCH3]2 (12).