单体双（η(2)-炔烃）铜（I）和银（I）的卤化物、拟卤化物及芳硫醇盐
Monomeric Bis(eta(2)-alkyne)copper(I) and -silver(I) Halides, Pseudohalides, and Arenethiolates.
作者信息
Janssen Maurits D., Herres Mathias, Zsolnai Laszló, Spek Anthony L., Grove David M., Lang Heinrich, van Koten Gerard
机构信息
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.
出版信息
Inorg Chem. 1996 Apr 24;35(9):2476-2483. doi: 10.1021/ic950710j.
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.
描述了配合物[(η⁵-C₅H₄SiMe₃)₂Ti(C≡CSiMe₃)₂]MX（M = Cu，X = OTf（2）、SC₆H₅（4）、SC₆H₄NMe₂ - 2（5）、SC₆H₄CH₂NMe₂ - 2（6）、S - 1 - C₁₀H₆NMe₂ - 8（7）、Cl（8）、(N≡CMe)PF₆（9）；M = Ag，X = OTf（3））的合成与表征。这些配合物包含单体MX实体，它们通过有机金属双（炔烃）配体[(η⁵-C₅H₄SiMe₃)₂Ti(C≡CSiMe₃)₂]（1）的两个炔烃官能团以η²键合。2与路易斯碱N≡CPh和N≡CC(H)=C(H)C≡N反应分别得到阳离子配合物{[(η⁵-C₅H₄SiMe₃)₂Ti(C≡CSiMe₃)₂]Cu(N≡CPh)}OTf（10）和{[(η⁵-C₅H₄SiMe₃)₂Ti(C≡CSiMe₃)₂]Cu}₂(N≡CC(H)=C(H)C≡N)(OTf)₂（11）。已测定了2、3和6的X射线结构。2的晶体为单斜晶系，空间群P2(1)/c，a = 12.8547(7) Å，b = 21.34(2) Å，c = 18.279(1) Å，β = 133.623(5)°，V = 3629.7(5) ų，Z = 4，对于5531个I≥2.5σ(I)的反射和400个变量，最终R = 0.047。三氟甲磺酸银配合物3与相应的铜配合物2同构但不同晶，3的晶体为单斜晶系，空间群P2(1)/c，a = 13.384(3) Å，b = 24.55(1) Å，c = 13.506(3) Å，β = 119.21(2)°，V = 3873(2) ų，Z = 4，对于3578个F≥4σ(F)的反射和403个变量，最终R = 0.038。铜芳硫醇盐配合物6的晶体为三斜晶系，空间群P-1，a = 11.277(3) Å，b = 12.991(6) Å，c = 15.390(6) Å，α = 65.17(4)°，β = 78.91(3)°，γ = 84.78(3)°，V = 2008(2) ų，Z = 2，对于6022个反射和388个变量，最终R = 0.079。配合物2 - 11均包含单体双（η²-炔烃）M(η¹-X)单元（M = Cu，Ag），其中第11族金属原子由螯合双（η²-炔烃）实体Ti(C≡CSiMe₃)₂和一个η¹键合的单阴离子配体X以三角方式配位。铜芳硫醇盐配合物4 - 7在溶液中是流动的。
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