ChemInform Abstract: MOLECULAR COMPLEXES. PART XXIII. CRYSTAL AND MOLECULAR STRUCTURES OF α-NAPHTHOL-1,2,4,5-TETRACYANOBENZENE AND β-NAPHTHOL-1,2,4,5-TETRACYANOBENZENE

1978 ◽  
Vol 9 (22) ◽  
Author(s):  
M. C. COULDWELL ◽  
K. PROUT
1990 ◽  
Vol 45 (10) ◽  
pp. 1369-1382 ◽  
Author(s):  
Heindirk tom Dieck ◽  
Lutz Stamp

Diazadienes RN = CR′-CR′ = NR (DAD) form molecular complexes with copper(I) halides of composition (DAD)CuX, the structures of which vary from [(DAD)2Cu]+(CuCl2)⁻ with a non-tetrahedral bis(chelated) cation, over [(DAD)CuCl]2 with asymmetrically bridging chloro ligands to planar three-coordinate (DAD)CuCl. The composition of the isolated complexes depends on the relative concentrations or on the solvent. The “soft” coordination geometry of copper is underlined by the structure of the coordination polymer of composition (DAD)2Cu5Cl5, in which Cu atoms of coordination number 2, 3 and 4 and very irregular geometries are encountered and where the DAD ligands are exclusively bridging. Halide ions and sp2-nitrogen donors are very competitive. Bridging DAD ligands are also encountered in (DAD)Cu-Y with the less nucleophilic anions trifluoromethane-sulphonate or perchlorate. Crystal and molecular structures are established for all these coordination geometries and the causes are discussed for the coordination flexibility of copper(I)


2003 ◽  
Vol 68 (9) ◽  
pp. 1647-1662 ◽  
Author(s):  
Valeria Amendola ◽  
Massimo Boiocchi ◽  
Yuri Diaz Fernandez ◽  
Carlo Mangano ◽  
Piersandro Pallavicini

The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.


2021 ◽  
Vol 60 (7) ◽  
pp. 5014-5020
Author(s):  
Yuji Tada ◽  
Atsushi Sunada ◽  
Riki Watanabe ◽  
Makoto Kanazawa ◽  
Keiichiro Utsumi

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