Activation of Perfluoro(methyl vinyl ether) at Rh(I) Complexes: Metal-Centered Versus Phosphine-Mediated Decarbonylation

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-05-12 DOI:10.1039/d5sc02056e

Soodeh Mollasalehi, Mike Ahrens, Thomas Braun

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Abstract

This study investigates the reactivity of perfluoro(methyl vinyl ether) [PMVE, CF₂=CF(OCF₃)] towards rhodium(I) phosphine complexes. The reaction pathways are characterized by C-O and C-F bond cleavage reactions and decarbonylation steps. On using the complex [Rh(H)(PEt₃)₃] (1), unprecedented reactivity pathways were observed that distinguish of those found for previously studied fluoroolefins. Reactivity of an excess PMVE at Rh is initiated by coordination to the Rh center in 1, followed by its insertion into the Rh-H bond and a b-OCF₃ elimination. This process ultimately results in OCF₃ ligand transformation to give trans-[Rh(F)(CO)(PEt₃)₃] (4) and Et₃PF₂. Reactions of stoichiometric amounts of PMVE with [Rh(H)(PEt₃)₃] (1) or excess amount of it with [Rh(F)(PEt₃)₃] (6) led to olefin complex formation to yield trans-[Rh(F)(η²-CF₂CFH)(PEt₃)₂] (7) and trans-[Rh(F)(CF(OCF₃)CF₂)(PEt₃)₂] (8), respectively. In contrast, a remarkable insertion into the Rh-F bond at [Rh(F)(CO)(PEt₃)₂] (4) was observed leading to the formation of trans-[Rh(CO)(CF(OCF₃)CF₃)(PEt₃)₂] (5). Decarbonylation of PMVE proceeds not only at Rh, but also via a metal-free, phosphine-mediated process. The latter is characterized by oxidative addition of PMVE at PEt₃ to form the fluorophosphoranes E/Z-(F₃CO)CF=CF(PFEt₃), which subsequently convert into Et₃PF₂, CO and presumably tetrafluoroethene.

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全氟（甲基乙烯醚）在Rh(I)配合物上的活化：金属中心与膦介导的脱碳反应

研究了全氟（甲基乙烯醚）[PMVE, CF2=CF(OCF3)]对膦铑配合物的反应性。反应途径以C-O和C-F键裂解反应和脱羰反应为特征。在使用配合物[Rh(H)(PEt3)3](1)时，观察到前所未有的反应途径，区别于先前研究的氟烯烃。过量的PMVE在Rh上的反应性是通过与1中的Rh中心配位开始的，随后插入Rh- h键并消除b-OCF3。这一过程最终导致OCF3配体转化为反式[Rh(F)(CO)(PEt3)3](4)和Et3PF2。化学计量量的PMVE与[Rh(H)(PEt3)3](1)或过量的PMVE与[Rh(F)(PEt3)3](6)反应生成烯烃络合物，分别生成反式-[Rh(F)(η - cf2cfh)(PEt3)2](7)和反式-[Rh(F)(CF(OCF3)CF2)(PEt3)2](8)。相反，在[Rh(F)(CO)(PEt3)2](4)处的Rh-F键显著插入导致反式-[Rh(CO)(CF(OCF3)CF3)(PEt3)2](5)的形成。PMVE的脱碳不仅在Rh上进行，而且通过一个无金属的、膦介导的过程进行。后者的特征是在PEt3上氧化加成PMVE，形成氟磷烷E/Z-(F3CO)CF=CF(PFEt3)，随后转化为Et3PF2、CO和四氟乙烯。

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.