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Graphical abstract Equimolar reactions of copper(I) halides with PPh 3 and pyridine-2-carbaldehyde-N-substituted thiosemicarbazone (C 5 H 4 N)HC2 N3N2(H)-C1(S)N1HR has yielded complexes, [CuX 2 (κS1-H 2 L1-R)(PPh 3)] 1–5 (X = halogen, R = Me, Et) with pyridine protonated thio-ligand. Similar reactions of copper(I) halides with benzaldehyde-N1-substituted thiosemicarbazones (C 6 H 5)HC2 N3-N2(H)-C1(S)-N1HR and Ph 3 P halogen bridged dinuclear complexes, [Cu 2 (μ-X) 2 (κS1-HL2-R) 2 (Ph 3 P) 2 ] 6–10 (X = halogen, R = Me, Et) or sulfur-bridged dinucelar complexes [Cu 2 (μ-S-HL2-Ph) 2 (κS1-HL2-Ph) 2 X 2 ] 11–13 with no Ph 3 P coordination. The substitutions at N1, C2 and order of reactants with change in solvent appear to have yielded three types of products. Abstract Equimolar reaction of copper(I) iodide with PPh 3 in acetonitrile formed compound of empirical composition, {CuI(Ph 3 P)} and its further reaction in chloroform with pyridine-2-carbaldehyde-N-methyl thiosemicarbazone {(C 5 H 4 N)HC2 N3-N2-(H)-C1(S)N1HR; R = Me; HL1-Me} formed crystals of complex, [CuICl(Ph 3 P)(κS1-H 2 L1-Me] 1a , tetramer [Cu 4 I 4 (Ph 3 P) 4 ] 1b and free HL1-Me 1c , separated from the same reaction vessel. The formation of product 1a involved abstraction of chlorine from chloroform and has pyridine-N-protonated thio-ligand. Copper(I) bromide/chloride with Ph 3 P and HL1-Me or HL1-Et also formed pyridyl protonated, [CuBr 2 (Ph 3 P)(κS1-H 2 L1-Me)] 2 , [CuCl 2 (Ph 3 P)(κS1-H 2 L1-Me)] 3 , [CuBr 2 (Ph 3 P)(κS1-H 2 L1-Et)] 4 and [CuCl 2 (Ph 3 P)(κS1-H 2 L1-Et)] 5. The products similar to 1b and 1c were also identified in these reactions. In these four coordinated complexes the pyridine protonated thio-ligands are coordinating through sulfur only. Copper(I) halides with benzaldehyde-N1-substituted thiosemicarbazones {(C 6 H 5)HC2 N3-N2(H)-C1(S)-N1HR ; R = Me, Et; HL2-Me; HL2-Et} and Ph 3 P have yielded halogen bridged dinuclear complexes, [Cu 2 (μ-X) 2 (κS1-HL2-R) 2 (Ph 3 P) 2 ] (X, R: I, Me, 6 ; Br, Me, 7 ; I, Et, 8 ; Br, Et, 9 ; Cl, Et, 10). For R = phenyl at N1 atom, copper(I) halides with two m moles of HL2-Ph have formed sulfur–bridged dinucelar complexes, namely, [Cu 2 (μ-S-HL2-Ph) 2 (κS1-HL2-Ph) 2 X 2 ] (X = I, 11 , Br, 12 , Cl, 13). Complexes have been characterized using analytical data, IR, proton NMR and single crystal X-ray crystallography (1–5, 7, 9, 11 and 12). The coordination environment of the Cu in complex 1a contains both Cl and I, but both sites are disordered. [ABSTRACT FROM AUTHOR]

The chemistry of copper(I) halides (CuX) with furan-2-carbaldehyde-N1-substituted thiosemicarbazones {(C4H3O)HC2N3N2H–C1(S)N1HR, Hftsc-N1HR} in presence of triphenyl phopshine is described. For methyl and ethyl substituents (R) at N1 atom, and with X = I, Br, Cl, the halogen-bridged dimers, namely, [Cu2(μ-X)2(η1-S-Hftsc-N1HR)2(PPh3)2] (R, X: Me, I, 1, Br 2, Cl 3; Et, I 4, Br 5, Cl 6) have been obtained.However, the presence of phenyl substituent at N1 has favored a three coordinate complex, [CuI(η1-S-Hftsc-N1HPh)2] 7, and with copper(I) bromide/and chloride, it has formed sulfur-bridged dimers, [Cu2X2(η1-Hftsc-N1HPh)2(μ-S-Hftsc N1HPh)2] (X = Br 8, Cl 9). In the latter three complexes (7–9), the Ph3P ligand did not take part in coordination. All these complexes have been characterized with the help of elemental analysis, IR, 1H NMR spectroscopy and X-ray crystallography (1–3, 5, 7 and 9). The bonding and nuclearity of complexes has been found to vary with the substituents at N1 atom. The intermolecular interactions have formed one dimensional (1, 9) and two dimensional (2, 3 and 5) networks. [ABSTRACT FROM AUTHOR]