Mononuclear Rh(II) PNP-type complexes. Structure and reactivity

Moran Feller, Eyal Ben-Ari, Tarkeshwar Gupta, Linda J.W. Shimon, Gregory Leitus, Yael Diskin-Posner, Lev Weiner, David Milstein

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Abstract

The Rh(II) mononuclear complexes [(PNPtBu)RhCl][BF4] (2), [(PNPtBu)Rh(OC(O)CF3)][OC(O)CF3] (4), and [(PNPtBu)Rh(acetone)][BF4]2 (6) were synthesized by oxidation of the corresponding Rh(I) analogs with silver salts. On the other hand, treatment of (PNPtBu)RhCl with AgOC(O)CF 3 led only to chloride abstraction, with no oxidation. 2 and 6 were characterized by X-ray diffraction, EPR, cyclic voltammetry, and dipole moment measurements. 2 and 6 react with NO gas to give the diamagnetic complexes [(PNPtBu)Rh(NO)Cl][BF4] (7) and [(PNPtBu)Rh(NO) (acetone)]-[BF4]2 (8) respectively. 6 is reduced to Rh(I) in the presence of phosphines, CO, or isonitriles to give the Rh(I) complexes [(PNPtBu)Rh(PR3)][BF4] (11, 12) (R = Et, Ph), [(PNPtBu)Rh(CO)][BF4] (13) and [(PNPtBu)Rh(L)] [BF4] (15, 16) (L = tert-butyl isonitrile or 2,6-dimethylphenyl isonitrile), respectively. On the other hand, 2 disproportionates to Rh(I) and Rh(III) complexes in the presence of acetonitrile, isonitriles, or CO. 2 is also reduced by triethylphosphine and water to Rh(I) complexes [(PNP tBu)RhCl] (1) and [(PNPtBu)Rh(PEt3)][BF 4] (11). When triphenylphosphine and water are used, the reduced Rh(I) complex reacts with a proton, which is formed in the redox reaction, to give a Rh(III) complex with a coordinated BF4, [(PNP tBu)Rh(Cl)(H)(BF4)] (9).

Original languageEnglish
Pages (from-to)10479-10490
Number of pages12
JournalInorganic Chemistry
Volume46
Issue number25
DOIs
Publication statusPublished - Dec 10 2007

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Feller, M., Ben-Ari, E., Gupta, T., Shimon, L. J. W., Leitus, G., Diskin-Posner, Y., Weiner, L., & Milstein, D. (2007). Mononuclear Rh(II) PNP-type complexes. Structure and reactivity. Inorganic Chemistry, 46(25), 10479-10490. https://doi.org/10.1021/ic701044b