DINUCLEAR METAL-COMPLEXES WITH SATURATED AND UNSATURATED HYDROCARBON BRIDGES

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)(5)M-( 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) 1 d and 1e the diesters [H3CO(O)C(CH2)(m)C(O)OCH3] [m=8, 9 (4d,e)] are o btained in a one-pot reaction. The unsaturated hydrocarbon bridged rhe nium 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 det ermined by an X-ray structural analysis. Crystal data for 8: space gro up P2(1)/n with a=12.501(2), b=6.592(2), c=26.875(5) Angstrom, beta=93 .28(2)degrees, V=2211.0(9) Angstrom(3), Z=4. The structure was refined to R=0.039, wR=0.090. (C) 1997 Elsevier Science S.A.