Photochemical synthesis of a zirconium cyclobutadienyl complex
Photochemical synthesis of a zirconium cyclobutadienyl complex
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DOI：
10.1039/d0cc01104e
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发表时间：
2020-05-18
影响因子：
4.9
通讯作者：
Milsmann, Carsten
中科院分区：
文献类型：
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作者：
Do, P. Minh N.;Akhmedov, Novruz G.;Milsmann, Carsten
((PMPMe)-P-Me)(2)ZrBn2((PMPMe)-P-Me=3，5-二甲基-2-(2-吡啶基)吡咯烷)在二苯乙炔的存在下，通过两个烯烃在低价锆中间体上的形式[2+2]环加成反应，得到第一个ETA(4)-环丁二烯基锆络合物((PMPMe)-P-Me)(2)Zr(ETA(4)-C4Ph4)。这种独特的反应性扩大了传统上产生锆环戊二烯的低价锆中心的炔偶联反应的范围。
Photolysis of ((PMPMe)-P-Me)(2)ZrBn2 ((PMPMe)-P-Me = 3,5-dimethyl-2-(2-pyridyl)pyrrolide) in the presence of diphenylacetylene yields the first eta(4)-cyclobutadienyl zirconium complex, ((PMPMe)-P-Me)(2)Zr(eta(4)-C4Ph4), through formal [2+2] cycloaddition of two alkynes at a putative low-valent zirconium intermediate. This unique reactivity expands the scope of alkyne coupling reactions at low-valent zirconium centers that traditionally produce zirconacyclopentadienes.