Preparation and Activation of Complexes of the Type [((mesityl)NCH2CH2)2NX]ZrMe2 (X = H, Me) with [Ph3C][B(C6F5)4] or [PhNMe2H][B(C6F5)4]
Preparation and Activation of Complexes of the Type [((mesityl)NCH2CH2)2NX]ZrMe2 (X = H, Me) with [Ph3C][B(C6F5)4] or [PhNMe2H][B(C6F5)4]
复制标题
[((异三叉基)NCH2CH2)2NX]ZrMe2 (X = H, Me) 与 [Ph3C][B(C6F5)4] 或 [PhNMe2H][B(C6F5)4] 类型配合物的制备和活化
DOI：
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发表时间：
2000
期刊：
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通讯作者：
W. M. Davis
中科院分区：
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作者：
R. Schrock;Arturo L. Casado;Jonathan T. Goodman;Lan‐Chang Liang;and Peter J. Bonitatebus;W. M. Davis
二甲基锆配合物[N2 NX] ZrMe 2（N2 NX = [（MesNCH 2CH 2）2NX]; Mes = mesityl; X = H（1a），Me（1b））在固态下具有“mer”结构，其中酰胺氮占据三角双锥中的“轴向”位置。1B与1当量[Ph 3C][B（C6 F5）4]反应，然后加入乙醚，得到醚加合物{[N2 NMe]ZrMe（Et 2 O）}+（与[B（C6 F5）4]-作为阴离子），其X射线研究表明它是一种fac三角双锥物种，其中乙醚在顶端位置配位。1 B与1当量[PhNMe 2 H][B（C6 F5）4]反应生成{[N2 NMe]ZrMe（NMe 2 Ph）}[B（C6 F5）4]，其溶液NMR研究表明其结构类似于{[N2 NMe]ZrMe（Et 2 O）}+。加热{[N2 NMe]ZrMe（NMe 2 Ph）}[B（C6 F5）4]的溶液导致一个均三甲苯基邻甲基中的C-H活化并形成甲烷。1B与0.5当量的[Ph_3C][B（C_6F_5）_4]反应，生成[{[N_2NMe]ZrMe}_2（μ-Me）][B（C_6F_5）_4]（5 B）。X射线衍射研究表明，该化合物的晶体结构几乎为线性。
The zirconium dimethyl complexes [N2NX]ZrMe2 (N2NX = [(MesNCH2CH2)2NX]; Mes = mesityl; X = H (1a), Me (1b)), have “mer” structures in the solid state in which the amido nitrogens occupy “axial” positions in a trigonal bipyramid. The reaction of 1b with 1 equiv of [Ph3C][B(C6F5)4] followed by addition of diethyl ether yielded the ether adduct {[N2NMe]ZrMe(Et2O)}+ (with [B(C6F5)4]- as the anion), an X-ray study of which revealed it to be a fac trigonal-bipyramidal species in which the diethyl ether is coordinated in an apical position. The reaction of 1b with 1 equiv of [PhNMe2H][B(C6F5)4] led to {[N2NMe]ZrMe(NMe2Ph)}[B(C6F5)4], solution NMR studies of which suggest a structure analogous to that of {[N2NMe]ZrMe(Et2O)}+. Heating solutions of {[N2NMe]ZrMe(NMe2Ph)}[B(C6F5)4] led to C−H activation in one mesityl o-methyl group and formation of methane. The reaction of 1b with 0.5 equiv of [Ph3C][B(C6F5)4] yielded [{[N2NMe]ZrMe}2(μ-Me)][B(C6F5)4] (5b), an X-ray diffraction study of which revealed an almost linea...