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铑的氟卡宾、氟代烯烃和氟代次甲基配合物。

Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh.

作者信息

Pell Christopher J, Zhu Yanjun, Huacuja Rafael, Herbert David E, Hughes Russell P, Ozerov Oleg V

机构信息

Department of Chemistry , Texas A&M University , College Station , TX 77842 , USA . Email:

Department of Chemistry , Dartmouth College , Hanover , New Hampshire 03755 , USA.

出版信息

Chem Sci. 2017 Apr 1;8(4):3178-3186. doi: 10.1039/c6sc05391b. Epub 2017 Feb 16.

DOI:10.1039/c6sc05391b
PMID:28507693
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5414389/
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 CHF and CHF produced perfluoroalkylidene complexes (PNP)Rh[double bond, length as m-dash]CF and (PNP)Rh[double bond, length as m-dash]C(F)(CF). (PNP)Rh[double bond, length as m-dash]CF could also be obtained the reaction of (PNP)Rh(TBE) with MeSiCF/CsF, with an admixture of (PNP)Rh(CF), where TBE = -butylethylene. Abstraction of fluoride from these neutral (PNP)RhC F complexes was successful, although only abstraction from (PNP)Rh[double bond, length as m-dash]CF 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(CF) and [(PNP)Rh(CF)] isomers as well as comparisons between the electronic structure of the [double bond, length as m-dash]CF, CF, and [triple bond, length as m-dash]CF complexes and their hydrocarbon analogues.

摘要

该手稿报道了一系列小全氟碳配体与(PNP)Rh片段（其中PNP是二芳基氨基/双（膦）钳形配体）形成的配合物的合成、表征及电子结构分析。以(PNP)Rh(TBE)作为(PNP)Rh的来源，与CHF和CHF反应生成了全氟亚烷基配合物(PNP)Rh═CF和(PNP)Rh═C(F)(CF)。(PNP)Rh═CF也可通过(PNP)Rh(TBE)与MeSiCF/CsF反应得到，并伴有(PNP)Rh(CF)，其中TBE = -丁基乙烯。从这些中性的(PNP)RhC F 配合物中成功地脱去了氟，尽管只有从(PNP)Rh═CF中脱去氟才能明确鉴定出Rh产物[(PNP)Rh≡CF]。密度泛函理论计算研究允许比较(PNP)Rh(CF)和[(PNP)Rh(CF)]异构体的相对能量，以及═CF、CF和≡CF配合物及其烃类类似物的电子结构之间的比较。

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