Synthesis and complexation of superbulky imidazolium-2-dithiocarboxylate ligands.

The superbulky N-heterocyclic carbenes (NHCs) 2,6-bis(diphenylmethyl)-4-methylimidazol-2-ylidene (IDipMe) and its 4-methoxy analogue (IDipOMe) reacted instantaneously with carbon disulfide to afford the corresponding imidazolium-2-dithiocarboxylate zwitterions in high yields. These new dithiolate ligands were fully characterized and their coordination chemistry toward common Re(i) and Ru(ii) metal sources was thoroughly investigated. Neutral [ReBr(CO)(SC·NHC)] chelates featured three facially-arranged carbonyl groups on a distorted octahedron, whereas cationic [RuCl(p-cymene)(SC·NHC)]PF complexes displayed a piano-stool geometry. The molecular structures of the six new compounds revealed that the NHC·CS inner salts were highly flexible. Indeed, the torsion angle between their anionic and cationic moieties varied between ca. 63° in the free ligands and 3° in the ruthenium complexes. Concomitantly, the S-C-S bite angle underwent a contraction from 131° to 110-113° upon chelation. Computation of the %V parameter showed that the dithiocarboxylate unit of the NHC·CS betaines chiefly determined the steric requirements of the imidazolium moieties, irrespective of the metal center involved in the complexation. The replacement of the p-methyl substituents of IDipMe with p-methoxy groups in IDipOMe did not significantly affect the ligand bulkiness. The more electron-donating methoxy group led, however, to small changes in various IR wavenumbers used to probe the electron donor properties of the carbene moiety.