Document Type
Article
Publication Date
2-16-2017
Publication Title
Chemical Science
Department
Department of Chemistry
Abstract
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)RhCF2 and (PNP)RhC(F)(CF3). (PNP)RhCF2 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)RhCxFy complexes was successful, although only abstraction from (PNP)Rh]CF2 allowed unambiguous identification of the Rh product, [(PNP)Rh 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 =CF2,C2F4, and CF+ complexes and their hydrocarbon analogues.
DOI
10.1039/c6sc05391b
Dartmouth Digital Commons Citation
Pell, Christopher; Zhu, Yanjun; Huacuja, Rafael; Herbert, David; Hughes, Russell; and Ozerov, Oleg, "Fluorocarbene, Fluoroolefin, and Fluorocarbyne Complexes of Rh" (2017). Dartmouth Scholarship. 700.
https://digitalcommons.dartmouth.edu/facoa/700