DINUCLEAR MANGANESE AND RHENIUM COMPLEXES WITH MIXED ALIPHATIC-AROMATIC HYDROCARBON BRIDGES

The symmetrically hydrocarbon-bridged complexes (OC)5M-(CH2)n+1-X-(CH2 )n+1-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) n-CH2-OSO2CF3]2 [X = 1,4-C6H4, n = 1 (1a), n = 2 (1b); 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, r espectively. According to an X-ray structural analysis 8 a crystallize s in the triclinic space group P1BAR with Z = 2. Depending on the solv ent, the reaction of 7a with [Mn(CO)5]- affords also the cyclic carben e complex 10a. The behavior of the manganese compounds toward CO has b een 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[CH2CH 2C(O)OCH3]2 (12).