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dc.contributor.author
Gaviglio, Carina del Valle
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Ben David, Yehoshoa
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Shimon, Linda J. W.
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Doctorovich, Fabio
dc.contributor.author
Milstein, David
dc.date.available
2019-04-12T22:30:05Z
dc.date.issued
2009-03
dc.identifier.citation
Gaviglio, Carina del Valle; Ben David, Yehoshoa; Shimon, Linda J. W.; Doctorovich, Fabio; Milstein, David; Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes; American Chemical Society; Organometallics; 28; 6; 3-2009; 1917-1926
dc.identifier.issn
0276-7333
dc.identifier.uri
http://hdl.handle.net/11336/74336
dc.description.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).
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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No Corresponde
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Otras Ciencias Químicas
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2019-03-21T16:13:06Z
dc.journal.volume
28
dc.journal.number
6
dc.journal.pagination
1917-1926
dc.journal.pais
Estados Unidos
dc.journal.ciudad
Washington
dc.description.fil
Fil: Gaviglio, Carina del Valle. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
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Fil: Ben David, Yehoshoa. The Weizmann Institute Of Science; Israel
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Fil: Shimon, Linda J. W.. The Weizmann Institute Of Science; Israel
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Fil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
dc.description.fil
Fil: Milstein, David. The Weizmann Institute Of Science; Israel
dc.journal.title
Organometallics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/om8011536
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/om8011536
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