Dalton Transactions p. 4845 - 4851 (2012)
Update date:2022-08-25
Topics:
Lobana, Tarlok S.
Khanna, Sonia
Butcher, Ray J.
2-Benzoylpyridine thiosemicarbazone {R1R2C 2N2·N3H-C1(S)-N 4H2, R1 = py-N1, R2 = Ph; Hbpytsc} with copper(i) iodide in acetonitrile-dichloromethane mixture has formed stable CuII-I bonds in a dark green CuII iodo-bridged dimer, [Cu2II(μ-I)2(η 3-N1,N2,S-bpytsc)2] 1. Copper(i) bromide also formed similar CuII-Br bonds in a dark green Cu II bromo-bridged dimer, [Cu2II(μ-Br) 2(η3-N1,N2,S-bpytsc) 2] 3. The formation of dimers 1 and 3 appears to be due to a proton coupled electron transfer (PCET) process wherein copper(i) loses an electron to form copper(ii), and this is accompanied by a loss of -N3H proton of Hbpytsc ligand resulting in the formation of anionic bpytsc-. When copper(i) iodide was reacted with triphenylphosphine (PPh3) in acetonitrile followed by the addition of 2-benzoylpyridine thiosemicarbazone in dichloromethane (Cu:PPh3:Hbpytsc in the molar ratio 1:1:1), both CuII dimer 1 and an orange CuI sulfur-bridged dimer, [Cu2II2(μ-S-Hbpytsc)2(PPh 3)2] 2 were formed. Copper(i) bromide with PPh3 and Hbpytsc also formed CuII dimer 3 and an orange CuI sulfur-bridged dimer, [Cu2IBr2(μ-S-Hbpytsc) 2(PPh3)2] 4. While complexes 2 and 4 exist as sulfur-bridged CuI dimers, 1 and 3 are halogen-bridged. The central Cu2S2 cores of 2 and 4 as well as Cu2X 2 of 1 (X = I) and 3 (X = Br) are parallelograms. One set of Cu II-I and CuII-Br bonds are short, while the second set is very long {1, Cu-I, 2.565(1), 3.313(1) A; 3, Cu-Br, 2.391(1), 3.111(1) A}. The Cu...Cu separations are long in all four complexes {1, 4.126(1); 2, 3.857(1); 3, 3.227(1); 4, 3.285(1) A}, more than twice the van der Waals radius of a Cu atom, 2.80 A. The pyridyl group appears to be necessary for stabilizing the CuII-I bond, as this group can accept π-electrons from the metal. The Royal Society of Chemistry 2012.
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