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Reactivity of Tuck-over Titanium Oxo Complexes with Isocyanides
Organometallics ( IF 2.5 ) Pub Date : 2018-06-22 , DOI: 10.1021/acs.organomet.8b00212
María Gómez-Pantoja 1, 2 , Juan. I. González-Pérez 1, 2 , Avelino Martín 1, 2 , Miguel Mena 1, 2 , Cristina Santamaría 1, 2 , Manuel Temprado 2, 3
Affiliation  

The reactivity of the “tuck-over” species [Ti25-C5Me5)(CH2Ph)3(μ-η5-C5Me4CH2C)(μ-O)] (1) and [Ti25-C5Me5)(CH2CMe3)(μ-η5-C5Me4CH2C)(μ-CH2CMe2CH2)(μ-O)] (2) toward isocyanides has been examined both synthetically and theoretically. Treatment of 1 with the isocyanides RNC, R = Me3SiCH2, 2,6-Me2C6H3, tBu, iPr, leads to a series of η2-iminoacyl species (36) where the molecule of isocyanide inserts into one of the terminal metal–alkyl bonds. The analogous reaction of the “tuck-over” metallacycle species 2 with 2,6-Me2C6H3NC and tBuNC results in the initial insertion of one isocyanide into the terminal Ti–alkyl bond to form the iminoacyl complexes 7 and 8, followed by a second insertion into the metallacycle moiety to generate 9, in the case of tert-butylisocyanide. DFT calculations support the selective reactivity observed experimentally with a kinetic and thermodynamic preference for RNC insertion on the terminal alkyl groups bound to both metallic centers over the alternative insertion on the “tuck-over” ligand.

中文翻译:

缩合钛氧基配合物与异氰酸酯的反应性

该“折入结束”物质的反应性钛[Ti 2(η 5 -C 55)(CH 2 PH)3(μ-η 5 -C 54 CH 2Ç)(μ-O)] (1)和钛[Ti 2(η 5 -C 55)(CH 2 CME 3)(μ-η 5 -C 54 CH 2ç)(μ-CH 2 CME 2 CH 2)(μ -O)](2)已对合成异氰酸酯和理论上均进行了研究。的治疗1与异氰化物RNC,R =我3 SICH 2,2,6-ME 2 ç 6 ħ 3卜,PR,导致一系列的η 2 -iminoacyl物种(3 - 6其中分子)异氰化物插入末端金属-烷基键之一。“残留”金属环氧化物种类2与2,6-Me 2 C 6 H 3 NC和t的类似反应叔丁基异氰化物的情况下,BuNC导致一个异氰酸酯最初插入末端的Ti-烷基键中以形成亚氨基酰基络合物78,然后第二次插入金属环部分以生成9。DFT计算支持了实验观察到的选择性反应性,在动力学和热力学方面,RNC优先插入在与两个金属中心键合的末端烷基上,而不是“ Tuck-over”配体上的交替插入。
更新日期:2018-06-22
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