DINUCLEAR COPPER(I) COMPLEXES OF 24-MEMBERED BIBRACCHIAL TETRAIMINE SCHIFF-BASE MACROCYCLES DERIVED FROM 2,5-DIFORMYLTHIOPHENE

The synthesis of dinuclear copper(I) complexes of bibracchial tetraimi ne Schiff base macrocycles derived from the cyclocondensation of 2,5-d iformylthiophene and the amines N, N-bis-(2-aminoethyl)-2-phenylethyla mine, N, N-bis-(2-aminoethyl)-n-butylamine and N, N-bis-(2-aminoethyl) -t-butylamine is described. The structures of three such complexes are reported. The complex [Cu2L3(CH3CN)(2)](PF6)(2) . CH3CN crystallises in the monoclinic space group P2(1)/c and has unit-cell dimensions a = 15.897(4), b = 13.329(4), c = 21.999(5)Angstrom, beta = 90.85(2)degre es, Z = 4; the Cu-Cu separation is 5.201 Angstrom. The complex [Cu2L4( CH3CN)(2)](PF6)(2) . 0.64CH(3)CN crystallises in the monoclinic space group P2(1)/n and has unit-cell dimensions a = 17.243(5), b = 11.451(6 ), c = 26.534(8)Angstrom, beta = 100.08(2)degrees, Z = 4; the Cu-Cu se paration is 5.386 Angstrom. The complex [Cu2L6(CH3CN)(2)](PF6)(2) . CH 3CN crystallises in the triclinic space group P (1) over bar and has u nit-cell dimensions a = 13.122(3), b = 13.2116(3), c = 13.718(3)Angstr om, alpha = 104.92(3)degrees, beta = 91.96(3)degrees, gamma = 96.19(3) degrees, Z = 2; the Cu-Cu separation is 5.215 Angstrom. In each comple x there is a strongly bonded acetonitrile molecule coordinated to each copper atom. The reaction of[Cu2L3(CH3CN)(2)](PF6)(2) with carbon mon oxide is discussed. (C) 1998 Elsevier Science S.A.