期刊
ORGANOMETALLICS
卷 28, 期 23, 页码 6695-6706出版社
AMER CHEMICAL SOC
DOI: 10.1021/om900698x
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资金
- United States Army Research Office [W9111NF-05-1-0430, W9111NF-06-1-0147]
- National Science Foundation [CHE0645563]
- Robert A. Welch Foundation [F-1621]
To investigate effects of redox-active functional groups on the coordination chemistry and electronic properties of N-heterocyclic carbenes (NHCs), we prepared a series of complexes comprising 1,3-diferrocenylimidazolylidene and -benzimidazolylidene (1 and 2, respectively), 1-ferrocenyl-3-methyl- and 1, 3-diphenyl-5-ferrocenylbenzimidazolylidene (3 and 4, respectively), N,N'-diisobutyldiaminocarbene[3]ferrocenophane (FcDAC), and 1,3-dimesitylnaphthoquinoimidazolylidene (NqMes) ligands and coordinated [Ir(COD)Cl] (COD = 1,5-cyclooctadiene), [Ir-(CO)(2)Cl], and [M(CO)(5)] (M = Cr, Mo, W) units. The coordination chemistry of the aforementioned NHCs was investigated by X-ray crystallography, and their electronic properties were studied by NMR and IR spectroscopy, as well as electrochemistry. No significant variation in nu(CO) was observed among metal carbonyl complexes supported by 2-4 and FcDAC, indicating that the number (one vs two) or redox-active groups, the location (N atom vs backbone) of the redox-active group, and carbene ring identities (strained six-membered, nonaromatic vs five-membered, heteroaromatic) did not have a significant effect on ligand electron-donating ability. Because the shifts in nu(CO) upon oxidation of 1-3 and FcDAC were similar in magnitude but opposite in sign to NqMes, we conclude that the enhancement or attenuation of ligand donating is primarily Coulombic in origin (i.e., due to the molecule acquiring a positive or negative charge).
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