Synthesis and complexation of superbulky imidazolium-2-dithiocarboxylate ligands

Abstract

The superbulky N-heterocyclic carbenes (NHCs) 2,6-bis(diphenylmethyl)-4-methylimidazol-2-ylidene (IDip*Me) and its 4-methoxy analogue (IDip*OMe) 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)₃(S₂C·NHC)] chelates featured three facially-arranged carbonyl groups on a distorted octahedron, whereas cationic [RuCl(p-cymene)(S₂C·NHC)]PF₆ complexes displayed a piano-stool geometry. The molecular structures of the six new compounds revealed that the NHC·CS₂ 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_Bur parameter showed that the dithiocarboxylate unit of the NHC·CS₂ 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 IDip*Me with p-methoxy groups in IDip*OMe 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.