title: Reactivity of Dialumane and "Dialumene" Compounds toward Alkenes.
abstract: The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr2C6H3)NC(Me)}2](2-)) with stilbene and styrene afforded the oxidation/insertion products [L(thf)Al(CH(Ph)-CH(Ph))AlL] (2) and [L(thf)Al(CH(Ph)-CH2)Al(thf)L] (3), respectively. In the presence of Na metal, precursor 1 reacted with butadienes, possibly through the reduced "dialumene" or the "carbene-like" :AlL species, to yield aluminacyclopentenes [LAl(CH2C(Me)=C(Me)CH2)Na]n (4 a) and [Na(dme)3][LAl(CH2C(Me)=CHCH2)] (4 b, 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] (5). The possible mechanisms of the cycloaddition reactions were studied by using DFT computations.
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, CAS, Lanzhou 730000 (P.R. China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China).
authors.forename: Yanxia
authors.initials: Y
authors.lastname: Zhao
authors.forename: Yibo
authors.initials: Y
authors.lastname: Lei
authors.forename: Qingsong
authors.initials: Q
authors.lastname: Dong
authors.forename: Biao
authors.initials: B
authors.lastname: Wu
authors.forename: Xiao-Juan
authors.initials: XJ
authors.lastname: Yang
keywords: alkenes; aluminum; cycloaddition; insertion; reaction mechanisms