Cesium Reduction of a Lithium Diamidochloroberyllate

Cesium Reduction of a Lithium Diamidochloroberyllate
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二氨基氯铍酸锂的铯还原

DOI:
10.1021/acs.organomet.3c00519
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发表时间:
2024
期刊:
影响因子:
2.8
通讯作者:
Pearce K
Pearce K
中科院分区:
化学2区
文献类型:
--
作者:
Pearce K

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单质铯与二聚体氯代酸锂[{SiNDipp}BeClLi]2[{SiNDipp} = {CH2SiMe2N(Dipp)}2,其中Dipp = 2,6-二异丙基苯基,在c6d6中发生室温反应,导致芳烃溶剂活化。虽然,与早期对锂和金属钠还原的观察结果相反,无法证实有争议的苯苯酸铯的生成,但这一过程证实了先前的假设,即这种以铍为中心的溶剂活化也需要氢化铍的形成。在甲苯中进行的类似反应的研究进一步证实了这些观察结果,在这种情况下,提出的生成形式低氧化态的铍自由基阴离子中间体诱导了甲苯esp3c - h键的激活,并分离了聚合苯乙烯酸铯,[Cs({SiNDipp}BeCH2C6H5)]∞。
Room temperature reaction of elemental cesium with the dimeric lithium chloroberyllate [{SiNDipp}BeClLi]2[{SiNDipp} = {CH2SiMe2N(Dipp)}2, where Dipp = 2,6-di-isopropylphenyl, in C6D6results in activation of the arene solvent. Although, in contrast to earlier observations of lithium and sodium metal reduction, the generation of a mooted cesium phenylberyllate could not be confirmed, this process corroborates a previous hypothesis that such beryllium-centered solvent activation also necessitates the formation of hydridoberyllium species. These observations are further borne out by the study of an analogous reaction performed in toluene, in which case the proposed generation of formally low oxidation state beryllium radical anion intermediates induces activation of a toluenesp3C–H bond and the isolation of the polymeric cesium benzylberyllate, [Cs({SiNDipp}BeCH2C6H5)]∞.
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影响因子: 16.6
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