Diene Dissolution of the Heavier Alkaline Earth Metals
Diene Dissolution of the Heavier Alkaline Earth Metals
复制标题
DOI：
10.1002/ejic.201101342
复制
发表时间：
2012-02
影响因子：
2.3
通讯作者：
Olaf Michel;H. Kaneko;H. Tsurugi;Koji Yamamoto;K. Törnroos;R. Anwander;K. Mashima
中科院分区：
文献类型：
--
作者：
Olaf Michel;H. Kaneko;H. Tsurugi;Koji Yamamoto;K. Törnroos;R. Anwander;K. Mashima
碱金属和碱土金属在芳烃（“钾-萘”、“镁-蒽”）或（取代的）1，3-二烯的存在下被有效活化以产生明确定义的有机金属络合物。在这项研究中，单核二烯配合物的钙，锶，钡已合成利用定制的1，3-二烯。分离出配合物[M（2，3-二甲基-1，4-二甲苯基-1，3-丁二烯）（thf）4]（M = Ca，Sr），[Ca（2，3-二甲基-1，4-二萘基-1，3-丁二烯）（thf）4]，和{Ba[2，3-二甲基-1，4-双（2，4-二甲基苯基）-1，3-丁二烯]（thf）4}，并对其进行了X射线结构分析。而钙-和锶-二烯显示出近似的metallacylo-3-戊烯配位，钡（II）作为最大的非放射性金属（II）阳离子揭示了金属杂环-2，4-庚烯键在固态。钡（II）与硼酸三苯甲酯反应生成的二元配合物{[Ba（thf）_8][B（C_6F_5）_4]_2}证明了钡（II）可以容纳8个thf分子。
Alkaline and alkaline earth metals are efficiently activated in the presence of aromatic hydrocarbons (“potassium–naphthalene”, “magnesium–anthracene”) or (substituted) 1,3-dienes to produce well-defined organometallic complexes. In this study, mononuclear diene complexes of calcium, strontium, and barium have been synthesized by utilizing tailor-made 1,3-dienes. Complexes [M(2,3-dimethyl-1,4-ditolyl-1,3-butadiene)(thf)4] (M = Ca, Sr), [Ca(2,3-dimethyl-1,4-dinaphthyl-1,3-butadiene)(thf)4], and {Ba[2,3-dimethyl-1,4-bis(2,4-dimethylphenyl)-1,3-butadiene](thf)4} were isolated and fully characterized including X-ray structure analyses. Whereas the calcium– and strontium–dienes show an approximate metallacylo-3-pentene coordination, barium(II) as the largest nonradioactive metal(II) cation reveals metallacyclo-2,4-heptadiene bonding in the solid state. It is further shown that barium(II) can accommodate eight thf molecules as evidenced in the dicationic complex {[Ba(thf)8][B(C6F5)4]2}, obtained from the reaction of barium–diene with trityl borate.