Abstract :
[en] 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[middle dot]NHC)] chelates featured three facially-arranged carbonyl groups on a distorted octahedron, whereas cationic [RuCl(p-cymene)(S2C[middle dot]NHC)]PF6 complexes displayed a piano-stool geometry. The molecular structures of the six new compounds revealed that the NHC[middle dot]CS2 inner salts were highly flexible. Indeed, the torsion angle between their anionic and cationic moieties varied between ca. 63[degree] in the free ligands and 3[degree] in the ruthenium complexes. Concomitantly, the S-C-S bite angle underwent a contraction from 131[degree] to 110-113[degree] upon chelation. Computation of the %VBur parameter showed that the dithiocarboxylate unit of the NHC[middle dot]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.
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