SYNTHESIS OF MACROCYCLIC MERCURY(II) DERIVATIVES OF '-TRIMETHYLENEBIS(CIS-STILBENE-ALPHA,BETA-DITHIOL) AND TETRAMETHYLENEBIS(CIS-STILBENE-ALPHA,BETA-DITHIOL) WITH UNUSUAL STRUCTURES

The reaction of the ligand cis--S-C(Ph)=C(Ph)-S-[CH2]n-S-C(Ph)=C(Ph)-S - with n = 3 (dianion of 1) with HgCl2 in ethanol produces a yellow li nearly trinuclear, mu-S and mu-Cl-bridged complex of composition C62H5 2Cl2Hg3S8 (4), in which the central Hg(II) ion is in a near octahedral arrangement of four Hg-S and two Hg-Cl bonds, whereas the two termina l Hg(II) ions are tetracoordinated with three Hg-S bonds and one Hg-Cl bond in distorted tetrahedral arrangements. The two ligands are biden tate with respect to the terminal and central Hg(II) ions. The corresp onding ligand with n = 4 (dianion of 2) reacts with HgCl2 to yield a y ellow Hg(II) complex of composition C32H28HgS4 (5), in which the ligan d is tetradentate and in the trans-syn configuration. The Hg(II) ion i n the unit cell of 5 is pentacoordinated, due to symmetric dimerizatio n of two molecules of 2 by two weak coordinate Hg-S bonds of 3.442(2) angstrom length.