Synthesis and Crystal Structure of the Heterovalent Copper(I,II) π-Complex Cu7Br6.48Cl1.52 ⋅ 2C3N3(OC3H5)3

Abstract

Single crystals of the heterovalent Cu I , Cu II π , σ -complex Cu 7 Br 6.48 Cl 1.52 · 2 C 3 N 3 ( OC 3 H 5 ) 3 are synthesized by the ac electrochemical method from an ethanol solution containing 2,4,6-triallyloxy-1,3,5-triazine, CuCl 2 · 2 H 2 O, and CuBr 2 . The unit cell parameters of the crystals are: space group P , a = 8.271 (3) The copper and halogen atoms form unique moieties Cu 6 X 6 linked by bridging fragments [ Cu 2+ ( C 3 N 3 ( OC 3 H 5 ) 3 ) 2 ] X 2 into infinite chains. Each inorganic moiety Cu 6 X 6 is linked with four 2,4,6-triallyloxy-1,3,5-triazine molecules. The ligand molecule is coordinated to one Cu II atom through the nitrogen atom of the triazine cycle and to two Cu I atoms through the C=C bonds of two allyl groups. The Br content equal to 0.57 in the X(4) position linking the Cu I and Cu II atoms differs markedly from a value of 0.85-0.91 for the X(1), X(2), and X(3) positions linked only with the Cu(I) atoms.

Synthesis, transition metal chemistry and catalytic reactions of ferrocenylbis(phosphonite), [Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))2}2]

“…The allylic carbon-carbon (C16-C17) double bond distance is found to be 1.339 (15) Å which is shorter than the CvC bond distance [1.41 Å] observed in [Cu 2 Cl 2 (cyclooctadiene-1,5) 2 ] and longer than the uncoordinated CvC bond distance in complex 16 [1.302( 17) Å] indicating an interaction of moderate strength. [42][43][44] The molecular structure of 16 consists of a discrete [(AuCl) 2 (μ-PFcP)] species having a crystallographically imposed 2-fold rotation symmetry with the 2-fold axis passing through the iron atom and the midpoint of the Au1-Au2 vector. The ligand coordinates to the metal centers in an open bridging mode with Au1-P1 and Au1-Cl1 bond distances of 2.2067 (19) and 2.289(2) Å, respectively, which are similar to those found in the analogous complexes [Au 2 Cl 2 (μ-dppf)] 45 (Au-P = 2.226(1) and Au-Cl = 2.282(1) Å) and [{Fe(C 5 H 4 PR) 2 -P,P′}Au 2 Cl 2 (R = -OC 10 H 6 (μ-S)C 10 H 6 O-)] 16 (Au-P = 2.202(1) and Au-Cl = 2.284(1) Å).…”

Highly stable olefin–Cu(i) coordination oligomers and polymers

“…10 [Cu 4 Br 4 (TTT [Cu 2 Br 3 (1,3-Diallylbenzotriazolium)] ( 11) was obtained from the reaction of CuBr 2 and an alcoholic solution of 1,3diallylbenzotriazolium bromide under AC electrochemical conditions. 12 In the structure, the separate Cu 2 Br 2 dimers are bridged by the bromine atom to form infinite double-chains. The ligand is coordinated to two metal atoms of different inorganic chains through the CLC bonds of both allyl groups.…”