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

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 treat...

Descripción completa

Guardado en:

Detalles Bibliográficos
Publicado:	2009
Materias:	Aromatic rings Chloride abstractions Dinitrogen complexes Linear modes Methyl chlorides Nitrosyl complexes Nmr spectroscopies Pentacoordinate complexes Quantitative formations Rh complex Rhodium complexes Solvent coordinations Solvent interactions Square-pyramidal geometries Trimethylbenzene X-ray structures Chlorine compounds Ligands Nuclear magnetic resonance spectroscopy Rhodium Solid solutions Solvents Synthesis (chemical) Rhodium compounds
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02767333_v28_n6_p1917_Gaviglio http://hdl.handle.net/20.500.12110/paper_02767333_v28_n6_p1917_Gaviglio
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_02767333_v28_n6_p1917_Gaviglio
record_format	dspace
spelling	paper:paper_02767333_v28_n6_p1917_Gaviglio2023-06-08T15:25:56Z Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes Aromatic rings Chloride abstractions Dinitrogen complexes Linear modes Methyl chlorides Nitrosyl complexes Nmr spectroscopies Pentacoordinate complexes Quantitative formations Rh complex Rhodium complexes Solvent coordinations Solvent interactions Square-pyramidal geometries Trimethylbenzene X-ray structures Chlorine compounds Ligands Nuclear magnetic resonance spectroscopy Rhodium Solid solutions Solvents Synthesis (chemical) Rhodium compounds 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).© 2009 American Chemical Society. 2009 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02767333_v28_n6_p1917_Gaviglio http://hdl.handle.net/20.500.12110/paper_02767333_v28_n6_p1917_Gaviglio
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Aromatic rings Chloride abstractions Dinitrogen complexes Linear modes Methyl chlorides Nitrosyl complexes Nmr spectroscopies Pentacoordinate complexes Quantitative formations Rh complex Rhodium complexes Solvent coordinations Solvent interactions Square-pyramidal geometries Trimethylbenzene X-ray structures Chlorine compounds Ligands Nuclear magnetic resonance spectroscopy Rhodium Solid solutions Solvents Synthesis (chemical) Rhodium compounds
spellingShingle	Aromatic rings Chloride abstractions Dinitrogen complexes Linear modes Methyl chlorides Nitrosyl complexes Nmr spectroscopies Pentacoordinate complexes Quantitative formations Rh complex Rhodium complexes Solvent coordinations Solvent interactions Square-pyramidal geometries Trimethylbenzene X-ray structures Chlorine compounds Ligands Nuclear magnetic resonance spectroscopy Rhodium Solid solutions Solvents Synthesis (chemical) Rhodium compounds Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
topic_facet	Aromatic rings Chloride abstractions Dinitrogen complexes Linear modes Methyl chlorides Nitrosyl complexes Nmr spectroscopies Pentacoordinate complexes Quantitative formations Rh complex Rhodium complexes Solvent coordinations Solvent interactions Square-pyramidal geometries Trimethylbenzene X-ray structures Chlorine compounds Ligands Nuclear magnetic resonance spectroscopy Rhodium Solid solutions Solvents Synthesis (chemical) Rhodium compounds
description	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).© 2009 American Chemical Society.
title	Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
title_short	Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
title_full	Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
title_fullStr	Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
title_full_unstemmed	Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
title_sort	synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
publishDate	2009
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02767333_v28_n6_p1917_Gaviglio http://hdl.handle.net/20.500.12110/paper_02767333_v28_n6_p1917_Gaviglio
_version_	1768544864123748352

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

Ejemplares similares