Solvent dependent crystallization of a few Hg(II) thiocarboxylates

During the process of crystallization of newly synthesized heterobimetallic complexes [(Ph3P)2Cu(μ-SCOR)2Hg(SCOR)] [R = Ph (1), th (thiophene) (2)] Hg(II) thiocarboxylate complexes were isolated. In chloroform/diethyl ether a phosphine migration led to the formation of Hg(Ph3P)(SCOPh)2 (3) and Hg(Ph3P)(SCOth)2 (4) while in chloroform/n-hexane the binary Hg(II) complexes, Hg(SCOPh)2 (5) and Hg(SCOth)2 (6) were isolated. In another reaction a heterobimetallic complex, Hg(SCOPh)2TiCl4 (7) was obtained as the end product. Molecular structures of 3, 4 and 6 were studied by single crystal X-ray diffraction. The crystals of 4 provided an interesting example of polytopal isomerism. Structures and electronic transitions have been explained on the basis of DFT calculations.