105900-33-2Relevant articles and documents
Dinuclear copper(I) benzoato complexes binding isocyanides and azo compounds
Toth, Andras,Floriani, Carlo,Chiesi-Villa, Angiola,Guastini, Carlo
, p. 236 - 241 (2008/10/08)
The copper(I)-benzoato complex [Cu(PhCO2)]4 (1) is a source of the doubly bridged dimetallic unit [Cu2(μ-PhCO2)2] in reaction with many substrates. Reaction with isocyanides, which parallels the reaction with carbon monoxide, leading to a very labile compound, produces two different complexes depending on the reaction solvent. In ethanol the dimeric complex [Cu2(μ-PhCO2)2(p-MeC6H 4NC)2] (4) [v(CN) (Nujol) = 2152 cm-1], having the two copper(I) centers very close at 2.750 (2) A?, formed. A significant intermolecular interaction involving the copper(I) of one dimer and the carbon of the isocyanide ligand of another dimer establishes a tetrameric structure in the solid state [Cu?Cu = 2.860 (2) A?]. This intermolecular interaction does not occur in [Cu2(μ-PhCO2)2(p-MeC6H 4NC)3]·THF (5), which formed when the reaction between 1 and p-MeC6H4NC was carried out in THF [Cu?Cu = 3.020 (3) A?; v(CN) (Nujol) = 2145 and 2125 cm-1]. In both complexes 4 and 5 the isocyanide has a terminal and semibridging bonding mode. The reaction of 1 with azo compounds led to polymeric structures where the [Cu2(μ-PhCO2)2] dimers are bridged by the azo functionality, from the lone pairs at the nitrogen atoms. The steric hindrance of the azo compound seems to play the major role in determining the Cu:azo ratio and the structure of the complex. Benzo[c]cinnoline reacted with 1 to form [Cu2(μ-PhCO2)2(μ-benzo[c]cinnoline)] n (6), containing the almost planar eight-membered ring [Cu2(μ-PhCO2)2]. The Cu?Cu distances are in turn 2.788 (2) and 3.262 (2) A? along the polymeric chain. Phthalazine reacted with 1 to form [Cu2(n-PhCO2)2(μ-phthalazine) 2]n (7) for which a polymeric structure analogous to that of 6 is proposed. The structures of complexes 4-6 have been determined. Complex 4: space group P1 (triclinic); a = 13.278 (4) A?; b = 10.690 (3) A?; c = 10.412 (2) A?; α = 104.20 (2)°; β = 95.71 (3)°; γ = 104.75 (3)°; V = 1364.7 (7) A?3; Z = 2; Dcalcd = 1.47 g cm3. The final R factor was 0.044 (Rw = 0.046) for 2557 observed reflections. Complex 5: space group P1 (triclinic); a = 10.440 (2) A?; b = 19.408 (4) A?; c = 10.476 (2) A?; α = 96.77 (2)°; β = 106.20 (2)°; γ = 77.66 (2)°; V = 1987.4 (8) A?3; Z = 2; Dcalcd = 1.32 g cm-3. The final R factor was 0.048 for 3236 observed reflections. Complex 6: space group Pbcn (orthorhombic); a = 21.679 (3) A?; b = 9.408 (1) A?; c = 10.564 (2) A?; V = 2154.6 (5) A?3; Z = 4; Dcalcd = 1.69 g cm-3. The final R factor was 0.064 (Rw = 0.064) for 1402 observed reflections.