铂（II）烯炔环异构化催化：中间体与静止态
Platinum(II) Enyne Cycloisomerization Catalysis: Intermediates and Resting States.
作者信息
Nelsen D Luke, Gagné Michel R
机构信息
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290.
出版信息
Organometallics. 2009 Feb 23;28(4):950-952. doi: 10.1021/om801069s.
Abstract
In situ generated [(PPP)Pt]BF(4) (PPP = triphos) catalyzes the cycloisomerization of 1,6-enyne-ols by initiative pi-activation of the alkyne. This generates an isolable cationic Pt-alkenyl species which subsequently participates in turnover limiting protonolysis with in situ generated acid. This latter reactivity contrasts cationic Pt-alkyls which are more difficult to protonolyze. Mechanistic studies on isolated Pt-alkenyls, and deuterium labeling helped to elucidate the mechanistic details.
摘要
原位生成的[(PPP)Pt]BF(4)（PPP = 三膦）通过对炔烃的初始π-活化催化1,6-烯炔醇的环异构化反应。这产生了一种可分离的阳离子铂-烯基物种，该物种随后与原位生成的酸参与限制周转的质子解反应。后一种反应性与更难进行质子解的阳离子铂-烷基形成对比。对分离出的铂-烯基进行的机理研究以及氘标记有助于阐明机理细节。
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