Insertion reaction of carbon disulfide into copper-carbon bonds of aromatic organocopper(I) compounds, in the presence of 2,2′-bipyridine and 1,10-phenanthroline. X-ray diffraction structures of the [(CuS 3C- o-tolyl)phen], [(CuS 3C- o-tolyl) 2phen] and [Cu 2(S 3C- o-tolyl)(S 2C- o-tolyl)bipy] complexes

Abstract

In the presence of nitrogen chelating ligands (LL=2,2′-bipyridine, 1,10-phenanthroline) the insertion reaction of CS 2 into the copper-carbon bond of arylcopper(I) compounds (ArPh, o- and p-tolyl) gave adducts of Cu(I) dithiocarboxylates with LL, whose stoicheiometry depended upon the ligand and the aryl moiety. Co-formation of perthio and perthiodithio derivatives was suggested by hydrolysis of the rough products. The adducts were identified by comparison with authentic samples, prepared by other routes and characterized by IR spectra. Crystal structures were established by X-ray diffraction analyses for the [(CuS 3C- o-T)phen] ( I), [(CuS 3C- o-T) 2phen] ( II) and [Cu 2(S 3C- o-T)(S 2C- o-T)bipy] ( III) complexes. Crystal data: C 20H 15CuN 2S 3 ( I), space group P 1 with a = 14.135(3), b = 7.659(3), c = 9.115(3) Å, α=73.33(2), β=96.89(3), γ=96.73(3)° and Z=2; C 28H 22Cu 2N 2S 6 ( II), space group P 1 with a = 12.385(2), b = 11.865(3), c = 11.331(2) Å, α = 114.35(3), β = 89.48(2), γ = 105.75(2)° and Z = 2; C 26H 22Cu 2N 2S 5 ( III), space group P2 1/ n, a = 25.057(4), b = 10.188(3), c = 10.960(3) Å, β = 100.58(3)° and Z = 4. In I and II the original tetrameric structure of the copper perthiocarboxylate, under the action of the new LL ligand, turns to mononuclear and binuclear, respectively, according to the Cu:LL ratios. In I the metal atom is pseudo-tetrahedrally coordinated by two N atoms from phen and two S atoms from the bidentate chelating o-tolyldithiocarboxylate ligand; complex II can be considered arising from I by electrophilic attack of the trigonally arranged metal atom of an ‘additional’ CuS 3C- o-T chelate unit on the terminal perthio S atom of the tetrahedral moiety. In the structure of III, which is the first example of a perthiodithiocarboxylate with an ortho substituent in the aryl group, tetrahedral and trigonal arranged copper(I) atoms, doubly bridged by perthio- and dithioarylate groups, are present.