Attempts at generating metathesis-active Fe(IV) and Co(IV) complexes via the reactions of (silox)2M(THF)2, [(silox)3M][Na(THF)2] (M = Fe, Co), and related species with propellanes and triphenylboron
Attempts at generating metathesis-active Fe(IV) and Co(IV) complexes via the reactions of (silox)2M(THF)2, [(silox)3M][Na(THF)2] (M = Fe, Co), and related species with propellanes and triphenylboron
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尝试通过 (silox)2M(THF)2, [(silox)3M][Na(THF)2] (M=Fe, Co) 的反应生成复分解活性 Fe(IV) 和 Co(IV) 配合物
DOI：
10.1016/j.poly.2022.115656
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发表时间：
2022
期刊：
影响因子：
2.6
通讯作者：
MacMillan, Samantha N.
中科院分区：
文献类型：
--
作者：
George, Gregory M.;Wolczanski, Peter T.;MacMillan, Samantha N.
介绍了（silox）2M(THF)2(1-M, Fe, Co), [(silox)3M]Na(THF)2（2- m, Fe, Co）和（silox）3Fe(THF)(3)的综合合成，以及1-Co，2-Fe和2-Co的x射线结构研究。这些配合物暴露于1.1.1-丙烷（111P, C5H6）和1,3-脱氢adamantane (AdP)，这是已知的romp活性烷基烯与钌的前体，没有引起类似的反应性。共有28个配合物进行了111pin尝试，使“Fe（IV）”烷基烷能够进行某种形式的烯烃复分解，但没有成功。在最好的情况下，3-外置亚甲基环丁烯被证明是催化开环的。添加三苯基硼作为路易斯酸并不能促进推进剂金属络合物的形成，但adp的重排是不寻常的。此外，2-Fe催化111p3 -外置亚甲基环丁烯的转化，使其在Ph3B上加成2次，得到结构表征的产物Ph(κ-CH=CMeCH2BPh(cC4H4-1-Ph,3-CH2)(4)，该产物具有环丁基开环、迁移和苯基迁移的特点。
Metathetical syntheses of (silox)2M(THF)2(1-M, Fe, Co), [(silox)3M]Na(THF)2(2-M, Fe, Co), and (silox)3Fe(THF) (3) are presented, as are X-ray structural studies of1-Co,2-Fe, and2-Co. Exposure of these complexes to 1.1.1-propellane (111P, C5H6) and 1,3-dehydroadamantane (AdP), which are known progenitors of ROMP-active alkylidenes with ruthenium, failed to elicit similar reactivity. A total of 28 complexes were subjected to111Pin attempts to make “Fe(IV)” alkylidenes capable of some form of olefin metathesis with no success. At best, catalytic ring-opening to 3-exo-methylene cyclobutylidene was evidenced. The addition of triphenylboron as a Lewis acid failed to aid in metal complex formation of the propellanes, but an unusual rearrangement ofAdPwas noted. In addition,2-Fe catalyzed the conversion of111Pto 3-exo-methylene cyclobutylidene, which added twice to Ph3B, affording a structurally characterized product, Ph(κ-CH=CMeCH2BPh(cC4H4-1-Ph,3-CH2) (4), which features cyclobutyl-ring-opening, migration, and phenyl migration.