Monomeric Bis(eta(2)-alkyne)copper(I) and -silver(I) Halides, Pseudohalides, and Arenethiolates.
The synthesis and characterization of the complexes [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]MX (M = Cu, X = OTf (2), SC(6)H(5) (4), SC(6)H(4)NMe(2)-2 (5), SC(6)H(4)CH(2)NMe(2)-2 (6), S-1-C(10)H(6)NMe(2)-8 (7), Cl (8), (N&tbd1;CMe)PF(6) (9); M = Ag, X = OTf (3)) are described. These complexes 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&tbd1;CSiMe(3))(2)] (1). The reactions of 2 with the Lewis bases N&tbd1;CPh and N&tbd1;CC(H)=C(H)C&tbd1;N afford the cationic complexes {[(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]Cu(N&tbd1;CPh)}OTf (10) and {[(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C&tbd1;CSiMe(3))(2)]Cu}(2)(N&tbd1;CC(H)=C(H)C&tbd1;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) Å, b = 21.340(2) Å, c = 18.279(1) Å, beta = 133.623(5) degrees, V= 3629.7(5) Å(3), Z = 4, and final R = 0.047 for 5531 reflections with I >/= 2.5sigma(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) Å, b = 24.55(1) Å, c = 13.506(3) Å, beta = 119.21(2) degrees, V = 3873(2) Å(3), Z = 4, and final R = 0.038 for 3578 reflections with F >/= 4sigma(F) and 403 variables. Crystals of the copper arenethiolate complex 6 are triclinic, space group P&onemacr;, with a = 11.277(3) Å, b = 12.991(6) Å, c = 15.390(6) Å, alpha = 65.17(4) degrees, beta = 78.91(3) degrees, gamma = 84.78(3) degrees, V = 2008(2) Å(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)-alkyne) entity Ti(C&tbd1;CSiMe(3))(2) and an eta(1)-bonded monoanionic ligand X. The copper arenethiolate complexes 4-7 are fluxional in solution.
Janssen
Maurits D.
MD
Department of Metal Mediated Synthesis, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands, Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany, and Department of Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Herres
Mathias
M
Zsolnai
Laszló
L
Spek
Anthony L.
AL
Grove
David M.
DM
Lang
Heinrich
H
van Koten
Gerard
G