Tetraallylsilane π–Complexation: Synthesis and Structure of [Cu₅Cl₅(CH₂–CH=CH₂)₄Si]

Abstract

By alternating-current electrochemical technique, starting from CuCl 2 · 2H 2 O and tetraallylsilane (TAS), crystals of the π complex [Cu 5 Cl 5 (CH 2 ϪCHϭCH 2 ) 4 Si] (I) were obtained, FTIR characterized and structurally investigated. The structure of I is monoclinic, space group P2 1 /n, a ϭ 12.292(3), b ϭ 12.083(3), c ϭ 13.356(3) Å , β ϭ 90.19(3)°, V ϭ 1983.7(9) Å 3 [at 100(2) K], Z ϭ 4; * Prof. Dr. V. Olijnyk E-Mail: olijnyk@uni.opole.pl [a]

Coordination environment friendly silicon in copper(I) chloride π-complexes with tetravinylsilane and dimethyltetravinyldisiloxane

“…Secondly, a weakness of the third Cu-Cl bond may affect also the degree of self-assembly CuCl units. So none 2-D Cu n Cl n aggregate has been found in the olefin complexes with silicon ligands examined to date [41,13,14], and even the formation of 1-D motif here is complicated.…”

“…Therefore, we have made an effort to build small complexes with mono-, and oligomeric silicon-containing ligands as model of vinyl polysiloxane d 10 metal adducts. Some of such unsaturated molecules (tetraallylsilane and divinyltetramethyldisiloxane) have been already used for the construction of different copper(I) chloride complexes in our previous works [13,14]. As a continuation of the studies on the crystal engineering in CuCl-polysiloxanes systems we have employed tetravinylsilane (TVS) and 1,2-dimethyl-1,1,2,2-tetravinyldisiloxane (DMTVDS) to produce new complexes [Cu 4 Cl 4 (TVS)] (I) and [Cu 4 Cl 4 (DMTVDS)] (II).…”

Structurally Defined Allyl Compounds of Main Group Metals: Coordination and Reactivity

“…100 Single‐crystal X‐ray diffraction data on tetrakis(allyl) compounds of Group 14 (semi)metals is only available for Si in heterobimetallic [Cu 5 Cl 5 (C 3 H 5 ) 4 Si], which features allyl ligands in μ 2 ‐η 1 :η 2 coordination modes (Figure 8). 101…”

“… Section of the solid‐state structure of [Cu 5 Cl 5 (C 3 H 5 ) 4 Si], which forms a three‐dimensional coordination polymer in the solid state 101. Ellipsoids set at 50 % probability.…”

Bridging vs. Chelating Coordination Modes of Vinylsilanes in CuI π‐Complexes: Structure and Stability

“…For this reason, tetravinylsilane (TVS) bridges two Cu 4 Cl 4 units in the structure of [Cu 4 Cl 4 (TVS)],16 whereas a lack of one of the vinyl groups does not allow self‐assembling of Cu 2 Cl 2 dimers in 1 . On the other hand, tetraallylsilane (TAS), the molecule with a longer spacer arm, was found to be efficient for cross‐linking and formation of four inter‐Cu 5 Cl 5 ‐cluster bridges in the structure of complex [Cu 5 Cl 5 (TAS)] 17. Thus, it becomes possible to design optimal copper(I) halide oligomers using the organic component with required electronic properties, molecular symmetry and conformational flexibility.…”