Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes

Carina Gaviglio, Yehoshoa Ben-David, Linda J W Shimon, Fabio Doctorovich, David Milstein

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Abstract

Pincer-type linear nitrosyl Rh(I) complexes, Rh(PCPBu)(NO)][BF4] (2) and [Rh(PCPBuCH2)(NO)][BF,4] (8), are reported (PCPBu = 1,3-bis[(di-fer/-butylphosphino)methyl]-2,4,6-trimethylbenzene). Complex 2 was synthesized by reaction of the Rh(I) dinitrogen complex Rh(PCPBu)N 2 (1) with NOBF2, while treatment of the methyl chloride complex Rh(PCPBu)(CH3)Cl (7) with NOBF4 led to the formation of 8. Upon addition of CO, a linear bent nitrosyl equilibrium was established, both in solution and in the solid state, between the linear nitrosyl Rh(I) complex 2 and the bent nitrosyl Rh(III) complex [Rh(PCP'Bu)(NO)(CO)][BF4] (3). Addition of LiCl to complex 2 resulted in the quantitative formation of the bent nitrosyl complex Rh(PCPBu)(NO)(Cl) (4). An IR study of solvent interactions of the nitrosyl ligand of complex 2 in various solvents is also presented, showing a linear bent nitrosyl equilibrium induced by solvent coordination. Treatment of 4 with HBF4 · O(C2H5)2 led to chloride abstraction, with formation of complex 2. Upon addition of NOBF4 to the PNP Rh(I) complex [C5HN(CH2P- (tBu)2) 2Rh(CH3CN)]BF4 (5), the bent nitrosyl complex C5H3N(CH2P(tBu)2) 2Rh(CH3CN)(NO)][BF4]2 (6) was obtained. Employing 15NO-labeled complexes it is possible to assign the bent or linear modes of bonding of NO on the basis of 15N NMR spectroscopy. X-ray structures of all nitrosyl complexes reported here confirm that the tetracoordinate species are square-planar with a linear nitrosyl ligand occupying the position trans to the aromatic ring and the metal is Rh(I), whereas the pentacoordinate complexes adopt a square-pyramidal geometry with a bent apical nitrosyl coordinated to Rh(III).

Original languageEnglish
Pages (from-to)1917-1926
Number of pages10
JournalOrganometallics
Volume28
Issue number6
DOIs
Publication statusPublished - Mar 23 2009

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Rhodium
rhodium
reactivity
Carbon Monoxide
synthesis
Methyl Chloride
Ligands
methyl chloride
ligands
Nuclear magnetic resonance spectroscopy
Chlorides
Metals
chlorides
solid state
X rays
nuclear magnetic resonance
Geometry
rings
geometry
metals

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes. / Gaviglio, Carina; Ben-David, Yehoshoa; Shimon, Linda J W; Doctorovich, Fabio; Milstein, David.

In: Organometallics, Vol. 28, No. 6, 23.03.2009, p. 1917-1926.

Research output: Contribution to journalArticle

Gaviglio, C, Ben-David, Y, Shimon, LJW, Doctorovich, F & Milstein, D 2009, 'Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes', Organometallics, vol. 28, no. 6, pp. 1917-1926. https://doi.org/10.1021/om8011536
Gaviglio, Carina ; Ben-David, Yehoshoa ; Shimon, Linda J W ; Doctorovich, Fabio ; Milstein, David. / Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes. In: Organometallics. 2009 ; Vol. 28, No. 6. pp. 1917-1926.
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abstract = "Pincer-type linear nitrosyl Rh(I) complexes, Rh(PCPBu)(NO)][BF4] (2) and [Rh(PCPBuCH2)(NO)][BF,4] (8), are reported (PCPBu = 1,3-bis[(di-fer/-butylphosphino)methyl]-2,4,6-trimethylbenzene). Complex 2 was synthesized by reaction of the Rh(I) dinitrogen complex Rh(PCPBu)N 2 (1) with NOBF2, while treatment of the methyl chloride complex Rh(PCPBu)(CH3)Cl (7) with NOBF4 led to the formation of 8. Upon addition of CO, a linear bent nitrosyl equilibrium was established, both in solution and in the solid state, between the linear nitrosyl Rh(I) complex 2 and the bent nitrosyl Rh(III) complex [Rh(PCP'Bu)(NO)(CO)][BF4] (3). Addition of LiCl to complex 2 resulted in the quantitative formation of the bent nitrosyl complex Rh(PCPBu)(NO)(Cl) (4). An IR study of solvent interactions of the nitrosyl ligand of complex 2 in various solvents is also presented, showing a linear bent nitrosyl equilibrium induced by solvent coordination. Treatment of 4 with HBF4 · O(C2H5)2 led to chloride abstraction, with formation of complex 2. Upon addition of NOBF4 to the PNP Rh(I) complex [C5HN(CH2P- (tBu)2) 2Rh(CH3CN)]BF4 (5), the bent nitrosyl complex C5H3N(CH2P(tBu)2) 2Rh(CH3CN)(NO)][BF4]2 (6) was obtained. Employing 15NO-labeled complexes it is possible to assign the bent or linear modes of bonding of NO on the basis of 15N NMR spectroscopy. X-ray structures of all nitrosyl complexes reported here confirm that the tetracoordinate species are square-planar with a linear nitrosyl ligand occupying the position trans to the aromatic ring and the metal is Rh(I), whereas the pentacoordinate complexes adopt a square-pyramidal geometry with a bent apical nitrosyl coordinated to Rh(III).",
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N2 - Pincer-type linear nitrosyl Rh(I) complexes, Rh(PCPBu)(NO)][BF4] (2) and [Rh(PCPBuCH2)(NO)][BF,4] (8), are reported (PCPBu = 1,3-bis[(di-fer/-butylphosphino)methyl]-2,4,6-trimethylbenzene). Complex 2 was synthesized by reaction of the Rh(I) dinitrogen complex Rh(PCPBu)N 2 (1) with NOBF2, while treatment of the methyl chloride complex Rh(PCPBu)(CH3)Cl (7) with NOBF4 led to the formation of 8. Upon addition of CO, a linear bent nitrosyl equilibrium was established, both in solution and in the solid state, between the linear nitrosyl Rh(I) complex 2 and the bent nitrosyl Rh(III) complex [Rh(PCP'Bu)(NO)(CO)][BF4] (3). Addition of LiCl to complex 2 resulted in the quantitative formation of the bent nitrosyl complex Rh(PCPBu)(NO)(Cl) (4). An IR study of solvent interactions of the nitrosyl ligand of complex 2 in various solvents is also presented, showing a linear bent nitrosyl equilibrium induced by solvent coordination. Treatment of 4 with HBF4 · O(C2H5)2 led to chloride abstraction, with formation of complex 2. Upon addition of NOBF4 to the PNP Rh(I) complex [C5HN(CH2P- (tBu)2) 2Rh(CH3CN)]BF4 (5), the bent nitrosyl complex C5H3N(CH2P(tBu)2) 2Rh(CH3CN)(NO)][BF4]2 (6) was obtained. Employing 15NO-labeled complexes it is possible to assign the bent or linear modes of bonding of NO on the basis of 15N NMR spectroscopy. X-ray structures of all nitrosyl complexes reported here confirm that the tetracoordinate species are square-planar with a linear nitrosyl ligand occupying the position trans to the aromatic ring and the metal is Rh(I), whereas the pentacoordinate complexes adopt a square-pyramidal geometry with a bent apical nitrosyl coordinated to Rh(III).

AB - Pincer-type linear nitrosyl Rh(I) complexes, Rh(PCPBu)(NO)][BF4] (2) and [Rh(PCPBuCH2)(NO)][BF,4] (8), are reported (PCPBu = 1,3-bis[(di-fer/-butylphosphino)methyl]-2,4,6-trimethylbenzene). Complex 2 was synthesized by reaction of the Rh(I) dinitrogen complex Rh(PCPBu)N 2 (1) with NOBF2, while treatment of the methyl chloride complex Rh(PCPBu)(CH3)Cl (7) with NOBF4 led to the formation of 8. Upon addition of CO, a linear bent nitrosyl equilibrium was established, both in solution and in the solid state, between the linear nitrosyl Rh(I) complex 2 and the bent nitrosyl Rh(III) complex [Rh(PCP'Bu)(NO)(CO)][BF4] (3). Addition of LiCl to complex 2 resulted in the quantitative formation of the bent nitrosyl complex Rh(PCPBu)(NO)(Cl) (4). An IR study of solvent interactions of the nitrosyl ligand of complex 2 in various solvents is also presented, showing a linear bent nitrosyl equilibrium induced by solvent coordination. Treatment of 4 with HBF4 · O(C2H5)2 led to chloride abstraction, with formation of complex 2. Upon addition of NOBF4 to the PNP Rh(I) complex [C5HN(CH2P- (tBu)2) 2Rh(CH3CN)]BF4 (5), the bent nitrosyl complex C5H3N(CH2P(tBu)2) 2Rh(CH3CN)(NO)][BF4]2 (6) was obtained. Employing 15NO-labeled complexes it is possible to assign the bent or linear modes of bonding of NO on the basis of 15N NMR spectroscopy. X-ray structures of all nitrosyl complexes reported here confirm that the tetracoordinate species are square-planar with a linear nitrosyl ligand occupying the position trans to the aromatic ring and the metal is Rh(I), whereas the pentacoordinate complexes adopt a square-pyramidal geometry with a bent apical nitrosyl coordinated to Rh(III).

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