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

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Carbon Monoxide
acetone
reactivity
Acetone
oxidation
phosphines
Phosphines
water
acetonitrile
Oxidation
dipole moments
Water
Redox reactions
chlorides
silver
Dipole moment
analogs
salts
Silver
Cyclic voltammetry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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

Mononuclear Rh(II) PNP-type complexes. Structure and reactivity. / Feller, Moran; Ben-Ari, Eyal; Gupta, Tarkeshwar; Shimon, Linda J W; Leitus, Gregory; Diskin-Posner, Yael; Weiner, Lev; Milstein, David.

In: Inorganic Chemistry, Vol. 46, No. 25, 10.12.2007, p. 10479-10490.

Research output: Contribution to journalArticle

Feller, M, Ben-Ari, E, Gupta, T, Shimon, LJW, Leitus, G, Diskin-Posner, Y, Weiner, L & Milstein, D 2007, 'Mononuclear Rh(II) PNP-type complexes. Structure and reactivity', Inorganic Chemistry, vol. 46, no. 25, pp. 10479-10490. https://doi.org/10.1021/ic701044b
Feller M, Ben-Ari E, Gupta T, Shimon LJW, Leitus G, Diskin-Posner Y et al. Mononuclear Rh(II) PNP-type complexes. Structure and reactivity. Inorganic Chemistry. 2007 Dec 10;46(25):10479-10490. https://doi.org/10.1021/ic701044b
Feller, Moran ; Ben-Ari, Eyal ; Gupta, Tarkeshwar ; Shimon, Linda J W ; Leitus, Gregory ; Diskin-Posner, Yael ; Weiner, Lev ; Milstein, David. / Mononuclear Rh(II) PNP-type complexes. Structure and reactivity. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 25. pp. 10479-10490.
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title = "Mononuclear Rh(II) PNP-type complexes. Structure and reactivity",
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).",
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T1 - Mononuclear Rh(II) PNP-type complexes. Structure and reactivity

AU - Feller, Moran

AU - Ben-Ari, Eyal

AU - Gupta, Tarkeshwar

AU - Shimon, Linda J W

AU - Leitus, Gregory

AU - Diskin-Posner, Yael

AU - Weiner, Lev

AU - Milstein, David

PY - 2007/12/10

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N2 - 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).

AB - 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).

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