MONOMERIC BIS(ETA(2)-ALKYNE)COPPER(I) AND BIS(ETA(2)-ALKYNE)SILVER(I)HALIDES, PSEUDOHALIDES, AND ARENETHIOLATES

The synthesis and characterization of the complexes [(eta(5)-C(5)H(4)S iMe(3))(2)Ti(C=CSiMe(3))(2)]MX (M = Cu, X = OTf (2), SC6H5 (4), SC(6)H (4)NMe(2)-2 (5), SC(6)H(1)CH(2)NMe(2)-2 (6), S-1-C(10)H(6)NMe(2)-8 (7) , Cl (8), (N=CMe)PF6 (9); M = Ag, X = OTf (3)) are described. These co mplexes contain monomeric MX entities, which are eta(2)-bonded by both alkyne functionalities of the organometallic bis(alkyne) ligand [(eta (5)-C(5)H(4)SiMe(3))(2)Ti(C=CSiMe(3))(2)] (1). The reactions of 2 with the Lewis bases N=CPh and N=CC(H)=C(H)C=N afford the cationic complex es )-C(5)H(4)SiMe(3))(2)Ti(C=SiMe(3))(2)]Cu(N=Ph)}OTf (10) and Ti(C=CS iMe(3))(2)]Cu}(2)(N=CC(H)=C-(H)C=N)(OTf)(2) (11), respectively. The X- ray structures of 2, 3, and 6 have been determined. Crystals of 2 are monoclinic, space group P2(1)/c, with a = 12.8547(7) Angstrom, b = 21. 340(2) Angstrom, c = 18.279(1) Angstrom, beta = 133.623(5)degrees, V = 3629.7(5) Angstrom(3), Z = 4, and final R = 0.047 for 5531 reflection s with I greater than or equal to 2.5 sigma(I) and 400 variables, The silver triflate complex 3 is isostructural, but not isomorphous, with the corresponding copper complex 2, and crystals of 3 are monoclinic, space group P2(1)/c, with a = 13.384(3) Angstrom, b = 24.55(1) Angstro m, c = 13.506(3) Angstrom, beta = 119.21(2)degrees, V = 3873(2) Angstr om(3), Z = 4, and final R = 0.038 for 3578 reflections with F greater than or equal to 4 sigma(F) and 403 variables. Crystals of the copper arenethiolate complex 6 are triclinic, space group P<P(1)over bar>, wi th a = 11.277(3) Angstrom, b = 12.991(6) Angstrom, c = 15.390(6) Angst rom, alpha = 65.17(4)degrees, beta = 78.91(3)degrees, gamma = 84.78(3) degrees, V = 2008(2) Angstrom(3), Z = 2, and final R = 0.079 for 6022 reflections and 388 variables. Complexes 2-11 all contain a monomeric bis(eta(2)-alkyne)M(eta(1)-X) unit (M = Cu, Ag) in which the group 11 metal atom is trigonally coordinated by the chelating bis(eta(2)-alkyn e) entity Ti-(C=CSiMe(3))(2) and an eta(1)-bonded monoanionic ligand X . The copper arenethiolate complexes 4-7 are fluxional in solution.