0000000000214279
AUTHOR
Tomasz Dużak
Bridging vs. Chelating Coordination Modes of Vinylsilanes in CuIπ-Complexes: Structure and Stability
Two new copper(I) olefin complexes, [Cu6Cl6(MTrVS)2] (1) and [Cu2Cl2(DMVSP)2] (2), of tridentate bridging methyltrivinylsilane (MTrVS) and bidentate chelating 2-[dimethyl(vinyl)silyl]pyridine (DMVSP) have been synthesized and characterized by single-crystal X-ray structure analysis, IR and 1H NMR spectroscopy. It has been shown that using the alkenylsilanes with required electronic properties, molecular symmetry and conformational flexibility, it is possible to control the formation of optimal copper(I) halide oligomers. The obtained results, together with relevant literature data, also illustrate how the coordination mode of vinylsilanes is related to Cu–(C=C) bond strengthening and, conse…
Coordination environment friendly silicon in copper(I) chloride π-complexes with tetravinylsilane and dimethyltetravinyldisiloxane
Abstract Two crystal complexes of copper(I) chloride with tetravinylsilane (TVS) dimethyltetravinyldisiloxane (DMTVDS) were prepared and examined by IR spectroscopy and X-ray diffraction: sp. gr. P2/a, Z = 4, a = 13.428(1) A, b = 7.9584(7) A, c = 14.694(1) A for [Cu4Cl4(TVS)]; sp. gr. P21/c, a = 10.505(1) A, b = 13.487(1) A, c = 13.870(1) A for [Cu4Cl4(DMTVDS)]. The influence of the vinylsilicon ligands on the efficiency of the Cu⋯C C interaction is discussed. Thus, the consideration of dSi ← π∗C C ← dCu conjugate system may help to understand how the silicon π-acceptor properties influence on the degree of trigonal distortion of the Cu(I) coordination tetrahedron as well as on the inorgani…
Tetraallylsilane π-Complexation: Synthesis and Structure of [Cu5Cl5(CH2-CH=CH2)4Si]
By alternating-current electrochemical technique, starting from CuCl2·2H2O and tetraallylsilane (TAS), crystals of the π complex [Cu5Cl5(CH2–CH=CH2)4Si] (I) were obtained, FTIR characterized and structurally investigated. The structure of I is monoclinic, space group P21/n, a = 12.292(3), b = 12.083(3), c = 13.356(3) A, β = 90.19(3)°, V = 1983.7(9) A3 [at 100(2) K], Z = 4; R1 = 0.0379, wR2 = 0.1040 for 3583 reflections. The TAS molecule behaves as a tetradentate cross-bridged ligand linking four (Cu5Cl5)∞ fragments through the C=C bonds. The influence of the inorganic part and ligand symmetries combined with their conformational abilities on the overall crystal symmetry is discussed.