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Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh.
Pell, Christopher J; Zhu, Yanjun; Huacuja, Rafael; Herbert, David E; Hughes, Russell P; Ozerov, Oleg V.
Afiliación
  • Pell CJ; Department of Chemistry , Texas A&M University , College Station , TX 77842 , USA . Email: ozerov@chem.tamu.edu.
  • Zhu Y; Department of Chemistry , Texas A&M University , College Station , TX 77842 , USA . Email: ozerov@chem.tamu.edu.
  • Huacuja R; Department of Chemistry , Texas A&M University , College Station , TX 77842 , USA . Email: ozerov@chem.tamu.edu.
  • Herbert DE; Department of Chemistry , Texas A&M University , College Station , TX 77842 , USA . Email: ozerov@chem.tamu.edu.
  • Hughes RP; Department of Chemistry , Dartmouth College , Hanover , New Hampshire 03755 , USA.
  • Ozerov OV; Department of Chemistry , Texas A&M University , College Station , TX 77842 , USA . Email: ozerov@chem.tamu.edu.
Chem Sci ; 8(4): 3178-3186, 2017 Apr 01.
Article en En | MEDLINE | ID: mdl-28507693
The manuscript reports the synthesis, characterization, and analysis of electronic structure in a series of complexes of small perfluorocarbon ligands with the (PNP)Rh fragment (where PNP is a diarylamido/bis(phosphine) pincer ligand). Reactions of (PNP)Rh(TBE) as the source of (PNP)Rh with CHF3 and C2HF5 produced perfluoroalkylidene complexes (PNP)Rh[double bond, length as m-dash]CF2 and (PNP)Rh[double bond, length as m-dash]C(F)(CF3). (PNP)Rh[double bond, length as m-dash]CF2 could also be obtained via the reaction of (PNP)Rh(TBE) with Me3SiCF3/CsF, with an admixture of (PNP)Rh(C2F4), where TBE = tert-butylethylene. Abstraction of fluoride from these neutral (PNP)RhC x F y complexes was successful, although only abstraction from (PNP)Rh[double bond, length as m-dash]CF2 allowed unambiguous identification of the Rh product, [(PNP)Rh[triple bond, length as m-dash]CF]+. DFT computational studies allowed comparison of relative energies of (PNP)Rh(C2F4) and [(PNP)Rh(C2F3)]+ isomers as well as comparisons between the electronic structure of the [double bond, length as m-dash]CF2, C2F4, and [triple bond, length as m-dash]CF+ complexes and their hydrocarbon analogues.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chem Sci Año: 2017 Tipo del documento: Article Pais de publicación: Reino Unido
Texto completo
Añadir a Mi BVS
Imprimir
XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chem Sci Año: 2017 Tipo del documento: Article Pais de publicación: Reino Unido