SULFUR CHELATES .31. SYNTHESIS AND CHARACTERIZATION OF ARYL XANTHOGENS, XANTHATE ESTERS, AND ESTERS OF O-ARYL S-ALKYL THIOCARBONATES - SYNTHESIS AND SINGLE-CRYSTAL X-RAY STRUCTURE OF A POLYMERIC XANTHOGEN COMPLEX OF COPPER(I), [CUCL(S2COC6H4-4-CH3)2]N

The synthesis and characterization of aryl xanthogens are reported in this paper. These materials are readily formed by oxidation of the metal aryl xanthates.1,2 Attempts to prepare the analogous COS derivatives by a similar route failed, although esters of the O-aryl thiocarbonates were obtained by a less direct route. The reaction of the aryl xanthogens with CuCl leads to the formation of a copper(I) complex in which the thione sulfur atom of the xanthogen coordinates to the copper. Two such S atoms are bound to each Cu(I) atom. The overall structure is polymeric with the metallic portion containing discrete halide bridged Cu2Cl2S4 units. A pseudotetrahedral coordination exists about each Cu(I) atom with a Cu-Cu distance of 2.872 A. The Cu-Cl distances are 2.302 (6) and 2.430 (4) Å while the bonded Cu-S distances are 2.284 (5) and 2.330 (6) Å. The S-S distance in the disulfide portion of the structure is 2.070 (7) Å. The distance of the disulfide unit from Cu(I) is over 3.2 Å. The phenyl ring is tilted nearly perpendicular to the OCS2 plane in each subunit. Anisotropic refinement of the heavy atoms with isotropic refinement of the carbon positions has produced agreement parameters R=0.063, Rw=0.058 for 906 data in an orthorhombic cell, Z=8. © 1978, American Chemical Society. All rights reserved.