Complexes of copper(I) with aromatic compounds in aqueous solutions

Ligand Effects on the Chemical Activity of Copper(I) Complexes: Outer‐ and Inner‐Sphere Oxidation of CuIL

“…The results obtained for the self exchange of Cu 2+/+ aq [reaction (20)] are in very good agreement with those of Davies et al, [48] who obtained kЈ 11 (20) This observation suggests that the value used for kЈ 22 and the experimental approach used are adequate, although the value reported by Sisley and Jordan, [49] kЈ 11 + measured in the present study, which shows that kЈ 11 decreases with an increase in n. The value reported for n = 3-4 is orders of magnitude smaller than that for n = 2, and this observation is in agreement with the assumption that k 14 is very small and can be neglected.…”

“…Using these data and the measured rate constants for reaction (1) (neglecting the electrostatic work term, which is small for reactions of relatively large ions with small charges in solutions with a relatively high ionic strength) the self-exchange rate constants, kЈ 11 , of the Cu II L/Cu I L couples, reaction (18), were calculated by applying the Marcus cross relation. These results are summed up in Table 1.…”

“…only to reaction (5) and (2) The rate constants are summed up in Table 3. According to the Marcus theory, [43][44][45][46] for reactions proceeding by the outer-sphere mechanism, kЈ 12 , the rate constant of the cross reaction, reaction (1), depends on three parameters: the equilibrium constant of the cross reaction (K 12 ) and the electron self-exchange rate constants kЈ 11 [reaction (18)] and kЈ 22 (the electron self-exchange rate con-stant for the [(cyclam)Ni III/II (SO 4 ) 2 ] -/2-couple). The equilibria constants K 12 are known from the redox potentials of the different complexes.…”

Mechanism of Reduction of the Nitrite Ion by CuI Complexes

“…The stability constant of the (Cu ϩ NO 2 Ϫ ) complex suggests that nitrite binds to the copper via the nitrogen atom, as the stability constants of Cu I complexes with oxo-anions are expected to be considerably lower. [42,43] Experimental Section Materials and Methods: NaNO 2 , CuSO 4 , Cu 0 , NH 3 , L 1 (L 1 ϭ 2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane), acetonitrile, acetic acid, NaClO 4 , and HClO 4 were purchased from Aldrich. PN [4,4,5,5-tetramethyl-2-(1-pyryl)-2-imidazoline-1-oxyl 3-oxide] was prepared according to modified procedures, along with small amounts of 4,4,5,5-tetramethyl-2-(1-pyryl)-2-imidazoline.…”

Synthesis of Natural Products on Solid Phases via Copper‐Mediated Coupling: Synthesis of the Aristogin Family, Spiraformin A, and Hernandial

“…[75] We found that phenols can be converted into diaryl ethers in excellent yields when reacted with solid-supported halogenated aryls, [76] under conditions similar to the syntheses first published by Song et al (Scheme 1). [77][78][79] Scheme 1. Diaryl ether formation in solution.…”