Syntheses and X-Ray Crystal Structures of New Copper(I) and Silver(I) Complexes containing Thione Ligands

Abstract

The reaction of [(Ph 3 P) 2 CuCl] 2 with 4-amino-6methyl-1,2,4-triazine-thione-5-one (AMTTO, 1) in methanol and further recrystallization from methanol/acetone solution gives [(C 4 H 4 N 3 SON(=CMe 2 )Cu(PPh 3 ) 2 Cl] (2) as a neutral complex.[(C 4 H 4 N 3 SON(=CMe 2 )Ag(PPh 3 ) 2 ]NO 3 (4) can be obtained in excellent yield by the reaction of [(AMTTO) 2 Ag]NO 3 (3) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X-ray diffraction studies. Crystal data for 2 at ±80°C: space group P1 with a

Mono- and Binuclear Copper(I) Complexes of Thionucleotide Analogues and Their Catalytic Activity on the Synthesis of Dihydrofurans

“…The bond-length values are within the average of Cu–P (av. 2.290 Å), Cu–Cl (2.375 Å) and Cu–S (2.387 Å) bond lengths reported in the literature − for mixed-ligand copper­(I) chloride complexes with phosphines and thiones. Therefore, the TUC and MTUC ligands are chelating the Cu2 metal centers.…”

“…In general, the Cu–P or Cu–X bond lengths are in agreement with those found in similar structures. The average Cu–Cl bond distance is 2.375 Å, the corresponding one of Cu–Br is 2.501 Å, and that of Cu–I is 2.675 Å (Table ). ,, The average Cu–P bond distance is 2.290 Å in copper chloride complexes, 2.283 Å in copper bromide complexes, and 2.289 Å in copper iodide ones, while the average Cu–S is 2.387 Å in copper chloride complexes, 2.362 Å in copper bromide complexes, and 2.366 Å in copper iodide ones (Table ). ,− It is worth mentioning that the Cu–P and Cu–S bond distances are independent of the nature of the halogen ligand present in the complexes. The bond angles around the copper centers in the cases of 3 – 5 varied between 98° and 124°, with the higher distortion detected for the P–Cu–P angle due to the valence-shell electron-pair repulsions.…”