1. Redox-Active N-Heterocyclic Carbenes: Design, Synthesis, and Evaluation of Their Electronic Properties
- Author
-
Christopher W. Bielawski, Andrew G. Tennyson, Evelyn L. Rosen, Daphne H. Sung, Philip T. Cresswell, C. Daniel Varnado, Vincent M. Lynch, Dimitri M. Khramov, and Justin W. Kamplain
- Subjects
chemistry.chemical_classification ,Stereochemistry ,Organic Chemistry ,Infrared spectroscopy ,Metal carbonyl ,Electrochemistry ,Medicinal chemistry ,Coordination complex ,Inorganic Chemistry ,Design synthesis ,chemistry ,Group (periodic table) ,Redox active ,Physical and Theoretical Chemistry ,Electronic properties - Abstract
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)2Cl], 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 νCO was observed among metal carbonyl complexes supported by 2−4 and FcDAC, indicating that the number (one vs two) of redox-active groups, the location (N atom vs backbone) of the redox-active group...
- Published
- 2009
- Full Text
- View/download PDF