| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1306100 | Inorganica Chimica Acta | 2012 | 7 Pages |
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.
Graphical abstractDuring the process of crystallization of [(Ph3P)2Cu(SCOR)2Hg(SCOR)] novel Hg(II) thiocarboxylate complexes, Hg(SCOR)2, (Ph3P)Hg(SCOPh)2 and two polytopal isomers of (Ph3P)Hg(SCOth)2 were isolated.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Heterobimetallic complexes (Ph3P)2Cu(μ-SCOR)2Hg(SCOR) have been synthesized. ► These complexes disproportionate in solution. ► (Ph3P)Hg(SCOR)2 and Hg(SCOR)2 crystallized depending on solvent media. ► Two different structural motifs of (Ph3P)Hg(SCOth)2 are present in the crystal lattice. ► Electronic spectra of Hg(II) complexes have been studied.
