Dinuclear metal complexes with saturated and unsaturated hydrocarbon bridges

Article abstract of DOI:10.1016/S0022-328X(97)00048-X

The reaction of the bis(triflates) [Y-(CH₂)_m-Y] [Y = F₃CSO₃, m = 4, 6-9, 12, 14, 16 (1a-h)] with the carbonyl metalates M′[M(CO)₅] (M′ = Na, K; M = Mn, Re) affords the alkanediyl bridged metal complexes [(OC)₅M-(CH₂)_m-M(CO)₅] [m = 6-9, 12, 14, 16; M = Mn (2b-h) and m = 4, 6-9, 12, 14, 16; M = Re (3a-h)]. Starting with K[Mn(CO)₅] and the bis(triflates) 1d and 1e the diesters [H₃CO(O)C(CH₂)_mC(O)OCH₃] [m = 8, 9 (4d,e)] are obtained in a one-pot reaction. The unsaturated hydrocarbon bridged rhenium complexes trans-[Re]-(CH₂)₂-CH=CH-(CH₂)₂-[Re] (6), cis-[Re]-(CH₂)₃-CH=CH-(CH₂)₃-[Re] (8), and [Re]-(CH₂)_p-CH₂-C≡C-CH₂-(CH₂)_p-[Re] {[Re] = Re(CO)₅, p = 1, 3 (11, 12)} are formed by reaction of the bis(triflates) trans-Y-(CH₂)₂-CH=CH-(CH₂)₂-Y (5), cis-Y-(CH₂)₃-CH=CH-(CH₂)₃-Y (7), and Y-(CH₂)_p-CH₂-C≡C-CH₂-(CH₂)_p-Y [Y = F₃CSO₃, p = 1, 3 (9, 10)] with Na[Re(CO)₅] in THF. The structure of 8 was determined by an X-ray structural analysis. Crystal data for 8: space group P2₁/n with a = 12.501(2), b = 6.592(2), c = 26.875(5)A, β = 93.28(2)°, V = 2211.0(9)A³, Z = 4. The structure was refined to R = 0.039, wR = 0.090.