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使用[Rh(DPEphos)]催化剂对HB·NMeH进行脱氢聚合反应：NMeH的促进作用。

Dehydropolymerization of HB·NMeH Using a [Rh(DPEphos)] Catalyst: The Promoting Effect of NMeH.

作者信息

Adams Gemma M, Ryan David E, Beattie Nicholas A, McKay Alasdair I, Lloyd-Jones Guy C, Weller Andrew S

机构信息

Chemistry Research Laboratories, Mansfield Road, University of Oxford, Oxford OX1 3TA, United Kingdom.

Institute of Chemical Sciences, Heriot Watt University, Edinburgh EH14 4AS, United Kingdom.

出版信息

ACS Catal. 2019 Apr 5;9(4):3657-3666. doi: 10.1021/acscatal.9b00081. Epub 2019 Mar 11.

DOI:10.1021/acscatal.9b00081
PMID:30984472
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6454579/
Abstract

[Rh(κ-PP-DPEphos){ηη-HB(NMe)(CH) Bu}][BAr ] acts as an effective precatalyst for the dehydropolymerization of HB·NMeH to form -methylpolyaminoborane (HBNMeH) . Control of polymer molecular weight is achieved by variation of precatalyst loading (0.1-1 mol %, an inverse relationship) and use of the chain-modifying agent H: with ranging between 5 500 and 34 900 g/mol and between 1.5 and 1.8. H evolution studies (1,2-FCH solvent) reveal an induction period that gets longer with higher precatalyst loading and complex kinetics with a noninteger order in [Rh]. Speciation studies at 10 mol % indicate the initial formation of the amino-borane bridged dimer, [Rh(κ-PP-DPEphos)(μ-H)(μ-HBN=HMe)][BAr ], followed by the crystallographically characterized amidodiboryl complex [Rh(-κ-PP-DPEphos)(σ,μ-(HB)NHMe)][BAr ]. Adding ∼2 equiv of NMeH in tetrahydrofuran (THF) solution to the precatalyst removes this induction period, pseudo-first-order kinetics are observed, a half-order relationship to [Rh] is revealed with regard to dehydrogenation, and polymer molecular weights are increased (e.g., = 40 000 g/mol). Speciation studies suggest that NMeH acts to form the  precatalysts [Rh(κ-DPEphos)(NMeH)][BAr ] and [Rh(κ-DPEphos)(H)(NMeH)][BAr ], which were independently synthesized and shown to follow very similar dehydrogenation kinetics, and produce polymers of molecular weight comparable with [Rh(κ-PP-DPEphos){η-HB(NMe)(CH) Bu}][BAr ], which has been doped with amine. This promoting effect of added amine in situ is shown to be general in other cationic Rh-based systems, and possible mechanistic scenarios are discussed.

摘要

[Rh(κ-PP-DPEphos){ηη-HB(NMe)(CH)Bu}][BAr]作为将HB·NMeH脱氢聚合形成聚甲基氨基硼烷(HBNMeH)的有效预催化剂。通过改变预催化剂负载量(0.1 - 1 mol%，呈反比关系)以及使用链改性剂H来控制聚合物分子量，数均分子量在5500至34900 g/mol之间，分散度在1.5至1.8之间。氢气析出研究(1,2-FCH溶剂)表明，随着预催化剂负载量增加，诱导期变长，并且在[Rh]方面呈现非整数级的复杂动力学。在10 mol%下的物种形成研究表明，最初形成氨基硼烷桥联二聚体[Rh(κ-PP-DPEphos)(μ-H)(μ-HBN=HMe)][BAr]，随后是经晶体学表征的脒基二硼基配合物[Rh(-κ-PP-DPEphos)(σ,μ-(HB)NHMe)][BAr]。在四氢呋喃(THF)溶液中向预催化剂中加入约2当量的NMeH可消除该诱导期，观察到准一级动力学，在脱氢方面揭示了与[Rh]的半级关系，并且聚合物分子量增加(例如，数均分子量 = 40000 g/mol)。物种形成研究表明，NMeH作用形成预催化剂[Rh(κ-DPEphos)(NMeH)][BAr]和[Rh(κ-DPEphos)(H)(NMeH)][BAr]，它们已独立合成并显示出非常相似的脱氢动力学，并且产生的聚合物分子量与掺杂有胺的[Rh(κ-PP-DPEphos){η-HB(NMe)(CH)Bu}][BAr]相当。已表明添加胺的这种原位促进作用在其他阳离子Rh基体系中普遍存在，并讨论了可能的机理情况。

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