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首页> 外文期刊>Chemistry: A European journal >Hydrocarbon-Soluble Calcium Hydride:A 'Worker-Bee' in Calcium Chemistry
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Hydrocarbon-Soluble Calcium Hydride:A 'Worker-Bee' in Calcium Chemistry

机译：可溶于烃的氢化钙：钙化学中的“工蜂”

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摘要

The reactivity of the hydrocarbon-soluble calcium hydride complex [[CaH(dipp-nacnac)(thf)}2](1;dipp-nacnac = CH{(CMe)(2,6-iPr2-C6H3N)}2)with a large variety of substrates has been investigated.Addition of 1 to C=O and C=N functionalities gave easy access to calcium alkoxide and amide complexes.Similarly,reduction of the C=N bond in a cyanide or an isocyanide resulted in the first calcium aldimide complexes [Ca{N=C(H)-R}(dipp-nacnac)] and [Ca{C(H)=NR}-(dipp-nacnac)],respectively.Complex-ation of 1 with borane or alane Lewis acids gave the borates and alanates as contact ion pairs.In reaction with epoxides,nucleophilic ring-opening is observed as the major reaction.The high reactivity of hydrocarbon-soluble 1 with most functional groups contrasts strongly with that of insoluble CaH2,which is essentially inert and is used as a common drying agent.Crystal structures of the following products are presented:[{Ca{OC(H)Ph2}(dipp- nacnac)}2], [{Ca{N=C(H)Ph}(dipp-nacnac)}2],[{Ca{C(H)=NC(Me)2CH2C- (Me)3}(dipp-nacnac)}2],[{Ca{C(H)= NCy}(dipp-nacnac)}2], [Ca(dipp-nacnac)(thf)]~+ [H2BC8H14]~-and [{Ca-(O Cy)(dipp-nacnac)}2].The generally smooth and clean conversions of 1 with a variety of substrates and the stability of most intermediates against ligand exchange make 1 a valuable key precursor in the syntheses of a wide variety of beta-diketiminate calcium complexes.
机译：烃溶性氢化钙络合物[[CaH（dipp-nacnac）（thf）} 2]（1; dipp-nacnac = CH {（CMe）（2,6-iPr2-C6H3N）} 2）与已经研究了各种各样的底物。在C = O和C = N官能团上加1可以很容易地获得烷氧基钙和酰胺络合物。类似地，氰化物或异氰化物中C = N键的还原产生了第一个钙醛酰亚胺复合物[Ca {N = C（H）-R}（dipp-nacnac）]和[Ca {C（H）= NR}-（dipp-nacnac）]。分别与硼烷或烷烃络合1路易斯酸将硼酸酯和丙酸酯作为接触离子对。与环氧化物反应时，亲核开环是主要反应。具有大多数官能团的烃溶性1的高反应性与不溶性CaH2形成强烈反差。基本上是惰性的，被用作常见的干燥剂。提出了以下产物的晶体结构：[{Ca {OC（H）Ph2}（dip-nacnac）} 2]，[{Ca {N = C（H）Ph }（dipp-nacnac）} 2]，[{Ca {C（H）= NC（Me）2CH2C -（Me）3}（dipp-nacnac）} 2]，[{Ca {C（H）= NCy}（dipp-nacnac）} 2]，[Ca（dipp-nacnac）（thf）]〜+ [H2BC8H14 ]〜-和[{Ca-（O Cy）（dipp-nacnac）} 2]。具有多种底物的1的一般平稳转化和大多数中间体对配体交换的稳定性，使1成为了有价值的关键前体各种β-二酮化钙络合物的合成。

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