Copper(I) nitrile complexes, part IV. Mechanism of copper(II) acetate and trifluoroacetate reduction by copper in acetonitrile in the presence of free carboxylic acid

Structural diversity and photoluminescence of copper(I) carboxylates: From discrete complexes to infinite metal-based wires and helices

“…14) spans a very broad range from 660/622 nm (23) to 530 nm (24), and 512 nm (25) [33]. While the double-helical copper(I) 3,5-bis(trifluoromethyl)benzoate (22) falls into that range with max of 594 nm [19], the non-luminescent behavior of copper(I) pivalate (21) still requires some explanation [15].…”

“…As for the dinuclear core members, the tetranuclear type of structure is also characteristic for carboxylates with both aliphatic and aromatic substituents. Overall, tetranuclear copper(I) carboxylates exhibit four different types of packing in the solid state, which can be (20) 610 [21] Polynuclear-helices [Cu(O2CC(CH3)3]∞ (21) Quenched [15] [Cu(O2C(3,5-CF3)2C6H3)]∞ (22) 594 [19] [Cu(O2C(3-F)(5-CF3)C6H3)]∞ (23) 622,660 [33] [Cu(O2C(3-F)(5-CF3)C6H3)]∞ (24) 530 [33] [Cu(O2C(3-F)(5-CF3)C6H3)]∞ (25) 512 [33] ex is 350 nm for all compounds, except for 5 ( ex = 418 nm), 23 ( ex = 400 nm), and 25 ( ex = 325 nm).…”

“…(2) and (3)). For example, copper(II) acetate and trifluoroacetate can be reduced by copper(0) metal in acetonitrile in the presence of corresponding carboxylic acid [23]. Copper(I) formate and acetate were prepared by using sulfur dioxide and hydroxylammonium sulfate as reducing agents.…”

“…The first product (23) was obtained by sublimation-deposition procedures of copper(I) 3-fluoro-5-(trifluoromethyl)benzoate at 120 • C. Complex 23 crystallizes in the monoclinic P2/c space group with 15 independent copper(I) atoms in the asymmetric unit. Its structure consists of a long polymeric chain containing 11 Cu(I) centers bridged by carboxylate groups and two additional dinuclear copper(I) units, which are connected to the main chain by copper-copper and copper-oxygen interactions ( Fig.…”

Copper Lanthanide Phosphonate Cages: Highly Symmetric {Cu3Ln9P6} and {Cu6Ln6P6} Clusters with C3v and D3h Symmetry

“…The presence of [Cu(MeCN) 4 ] + could be explained as the reduction product of the [Cu 2 (O 2 C t Bu) 4 (HO 2 C t Bu) 2 ] in the presence of free carboxylic acid, as previously seen. 22 Similarly a family of highly symmetrical {Cu 6 Ln 6 P 6 } were obtained after refluxing [Cu 2 (O 2 C t Bu) 4 (HO 2 C t Bu) 2 ], [Ln 2 (O 2 C t Bu) 6 (HO 2 C t Bu) 6 ], and an amino-functionalized phosphonate source, (1-amino-1-methylethyl)phosphonic acid. Single crystal X-ray analysis revealed the products to be [Cu 6 Ln 6 (μ 3 -OH) 6 (O 3 PC(NH 2 )-Me 2 ) 6 (O 2 C t Bu) 12 ] in (20−36%) yield.…”