Synthesis of a Dialumene-Benzene Adduct and Its Reactivity as a Synthetic Equivalent of a Dialumene
Synthesis of a Dialumene-Benzene Adduct and Its Reactivity as a Synthetic Equivalent of a Dialumene
复制标题
DOI：
10.1002/anie.201305228
复制
发表时间：
2013-10-04
影响因子：
16.6
通讯作者：
Tokitoh, Norihiro
中科院分区：
文献类型：
--
作者：
Agou, Tomohiro;Nagata, Koichi;Tokitoh, Norihiro
含有较重主族元素的多重键合物质已被广泛研究，而含有13族元素的类似物质的化学反应仍处于起步阶段。[2,3]对于镓，[4]，铟，[5]和铊，[6]的同源物来说，具有RM= MR （M: Al, Ga, In, Tl）的可分离的中性重族13二金属烯的例子仍然很少，到目前为止，铝还没有发现。[7-9] 2003年，Power等人报道了1,2 -二芳基二铝A（方案1）的合成尝试化合物B的分离可能是由于ArAlI2的还原和随后的甲苯捕获产生了A。[11,12]同时，从高活性二铝烯合成子的角度来看，B等二铝烯-芳烃加合物的反应性很有趣，因为这些加合物有望与小分子反应，形成“Ar-Al= Al-Ar”结构，同时消除芳烃部分，因为芳烃稳定能增加。[13,14]本文报道了二铝苯加合物1的合成及其性质（方案2）。研究了1的反应性，并证明了1作为合成的二铝当量的性质。通过在苯中还原1,2 -二溴二铝烷3 (Scheme 2)，定量得到二铝苯加合物1为对空气和水分敏感的红色晶体。[15,16]通过x射线晶体学分析确定了1的固态结构（图1），从而显示了其
Multiply bonded species involving heavier main-group elements have been extensively investigated,[1] whereas the chemistry of analogous species involving group 13 elements is still in its infancy.[2, 3] Examples for isolable neutral heavier group 13 dimetallenes with the formula of RM= MR (M: Al, Ga, In, Tl) remain scarce for the homologues of gallium,[4] indium,[5] and thallium,[6] and have been unknown for aluminum so far.[7–9] In 2003, Power et al. reported the attempted synthesis of the 1, 2-diaryldialumene A (Scheme 1).[10] Isolation of the compound B is likely interpreted in terms of the generation of A by the reduction of ArAlI2 and subsequent trapping with toluene.[11, 12] Meanwhile, reactivities of dialumene-arene adducts such as B are interesting from the viewpoint of synthons for highly reactive dialumenes, since the adducts are expected to react with small molecules as an “Ar-Al= Al-Ar” building block along with elimination of the arene moiety as there is a gain in aromatic stabilization energies.[13, 14] Herein, we report the synthesis and properties of the dialumene-benzene adduct 1 (Scheme 2). The reactivities of 1 have been investigated, and demonstrate the properties of 1 as a synthetic equivalent of a dialumene.The dialumene-benzene adduct 1 was obtained quantitatively as air-and moisture-sensitive red crystals by the reduction of the 1, 2-dibromodialumane 3 in benzene (Scheme 2).[15, 16] The solid-state structure of 1 was determined by X-ray crystallographic analysis (Figure 1), thus showing its