SYNTHESIS AND REACTIVITY OF THE 1ST AG(I) PERTHIOCARBOXYLATES - CRYSTAL-STRUCTURES OF TETRA(ORTHO-TOLYLPERTHIOCARBOXYLATO)TETRA-SILVER(I), [AGS3C-ORTHO-TOLYL]4, AND OF ITS COCRYSTALLIZATION PRODUCT WITH COPPER(I), [AG1.76CU2.24(S3C-ORTHO-TOLYL)4]

Ag(I)-o-tolylperthiocarboxylate (I) and some Ag(I) arylperthiodithiocarboxylates were prepared by addition of AgNO3 to the product isolated from reaction of aldehydes and ammonium polysulfide in basic medium. The X-ray diffraction analysis of I showed that its structure consists of tetranuclear [Ag(S3- CC7H7)]4 complexes and is isomorphous with the corresponding Cu(I) derivative. Mixed crystals of the two pure molecular species, of microscopical structural uniformity, could be obtained. The X-ray diffraction analysis on a suitable crystal of these cocrystallized products yielded a formula [Ag1.76- Cu2.24(S3CC7H7)4] (II); the structure of II is isomorphous with the pure components. Crystals of I and II are both triclinic, space group P1, with a = 13.189(3), b = 13.085(3), c = 12.742(3) Å, α = 98.35(2), β = 85.28(2), γ = 75.71(2)° and Z = 2 for I; a = 12.727(2), b = 13.152(2), c = 12.860(3) Å, α = 103.93(2), β = 81.64(2), γ = 84.72(2)° and Z = 2 for II. Final R and Rw were respectively 5.53 and 7.03 for I and 3.73 and 4.94 for II. The CS3 group of the above compounds undergoes desulfuration by triphenylphosphine, giving, according to the stoichiometries of the reactions, the dithiocarboxylates or their complexes AgS2CAr(PPh3) and AgS2CSAr(PPh3)2. Some significant IR and NMR data for the above compounds are reported. © 1990.