MOLECULAR AND CRYSTAL-STRUCTURES OF NEW BINUCLEAR THIOOXALATE-BRIDGEDCOMPLEXES - (MU-TRITHIOOXALATO-S,S' S',S'')BIS[BIS(TRIPHENYLPHOSPHINE)SILVER(I)], THE FIRST VERIFIED SIMULTANEOUSLY END-ON SIDE-ON COORDINATED THIOOXALATE, AND ATO-S,O/S',O')BIS[BIS(TRIPHENYLPHOSPHINE)METAL(I)] (METAL=COPPER, SILVER)/

Synthesis, crystal and molecular structures of three binuclear complex es with bridging trithiooxalate (trto) or 1,1-dithiooxalate (i-dto) ar e reported. [(Ph(3)P)(2)Ag](2)(trto)(1) is triclinic, space group P $( $) over bar$$ 1 (No. 2) with Z = 2, a = 11.645(2) Angstrom, b = 13.473 (2) Angstrom, c = 23.304(5) Angstrom, alpha = 82.09(3)degrees, beta = 84.17(2)degrees, gamma = 64.41(1)degrees, and V = 3263(2) Angstrom(3). The compound represents the first authentic case of an end-on coordin ating thio-oxalate. One silver atom is side-on bound, whereas the othe r one links two sulfur atoms end-on leaving the oxalate oxygen non-coo rdinated. The bridging trto ligand exhibits a torsion angle along C-C of 50(1)degrees. [(Ph(3)P)(2)M](2)(i-dto) (M = Cu (2a), Ag (2b)) are m onoclinic, space group P2(1)/c (No. 14) with Z = 4, a = 23.629(2) Angs trom, b = 13.723(1) Angstrom, c = 20.512(2) Angstrom, beta = 104.06(1) degrees, and V = 6452(2) Angstrom(3) for M = Cu and a = 23.605(8) Angs trom, b = 13.737(4) Angstrom, c = 20.522(6) Angstrom, beta = 103.92(2) degrees, and V = 6459(6) Angstrom(3) for M = Ag. The bridging i-dto li gand links the metal c:enters side-on/side-on symmetrically, but is fa r from being planar showing a torsion angle along C-C of 19.3(5)degree s.