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路易斯碱性铂配合物对氟硼烷的反应性。

Reactivity of Lewis basic platinum complexes towards fluoroboranes.

机构信息

Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.

出版信息

Chemistry. 2013 Jul 1;19(27):8797-805. doi: 10.1002/chem.201301056. Epub 2013 May 15.

Abstract

We herein report detailed investigations into the interaction of Lewis acidic fluoroboranes, for example BF2Pf (Pf=perfluorophenyl) and BF2Ar(F) (Ar(F)=3,5-bis(trifluoromethyl)phenyl), with Lewis basic platinum complexes such as [Pt(PEt3)3] and [Pt(PCy3)2] (Cy=cyclohexyl). Two presumed Lewis adducts could be identified in solution and corresponding secondary products of these Lewis adducts were characterized in the solid state. Furthermore, the concept of frustrated Lewis pairs (FLP) was applied to the activation of ethene in the system [Pt(BPf3)(CH2CH2)(dcpp)] (dcpp=1,3-bis(dicyclohexylphosphino)propane; Pf=perfluorophenyl). Finally, DFT calculations were performed to determine the interaction between the platinum-centered Lewis bases and the boron-centered Lewis acids. Additionally, several possible mechanisms for the oxidative addition of the boranes BF3, BCl3, and BF2Ar(F) to the model complex [Pt(PMe3)2] are presented.

摘要

我们在此详细研究了路易斯酸氟硼烷(例如 BF2Pf(Pf=全氟苯基)和 BF2Ar(F)(Ar(F)=3,5-双(三氟甲基)苯基))与路易斯碱铂配合物(例如[Pt(PEt3)3]和[Pt(PCy3)2](Cy=环己基)之间的相互作用。可以在溶液中鉴定出两种假定的路易斯加合物,并在固态中对这些路易斯加合物的相应次级产物进行了表征。此外,还将受阻路易斯对(FLP)的概念应用于体系[Pt(BPf3)(CH2CH2)(dcpp)](dcpp=1,3-双(二环己基膦基)丙烷;Pf=全氟苯基)中乙烯的活化。最后,进行了 DFT 计算以确定铂中心路易斯碱与硼中心路易斯酸之间的相互作用。此外,还提出了硼烷 BF3、BCl3 和 BF2Ar(F) 与模型配合物[Pt(PMe3)2]进行氧化加成的几种可能机制。

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