Reactivity of Dialumane and "Dialumene" Compounds toward Alkenes. Issue 36 (18th July 2013)

• Record Type: Journal Article
• Authors: Zhao, Yanxia; Lei, Yibo; Dong, Qingsong; Wu, Biao; Yang, Xiao‐Juan
• Is Part Of: Chemistry. Volume 19:Issue 36(2013)
• Page Start: 12059
• Page End: 12066
• Publication Date: 2013-07-18
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201300735
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reactions of dialumane [L(thf)AlAl(thf)L] (<bold>1</bold>, L=[{(2, 6‐<italic>i</italic>Pr₂C₆H₃)NC(Me)}₂]²⁻) with stilbene and styrene afforded the oxidation/insertion products [L(thf)Al(CH(Ph)CH(Ph))AlL] (<bold>2</bold>) and [L(thf)Al(CH(Ph)CH₂)Al(thf)L] (<bold>3</bold>), respectively. In the presence of Na metal, precursor <bold>1</bold> reacted with butadienes, possibly through the reduced "dialumene" or the "carbene‐like" :AlL species, to yield aluminacyclopentenes [LAl(CH₂C(Me)C(Me)CH₂)Na]_{<italic>n</italic>} (<bold>4 a</bold>) and [Na(dme)₃][LAl(CH₂C(Me)CHCH₂)] (<bold>4 b</bold>, dme=dimethoxyethane) as [1+4] cycloaddition products, as well as the [2+4] cycloaddition product 1, 6‐dialumina‐3, 8‐cyclodecadiene, [{Na(dme)}₂][LAl(CH₂C(Me)C(Me)CH₂)₂AlL] (<bold>5</bold>). The possible mechanisms of the cycloaddition reactions were studied by using DFT computations.</p> </abstract>