Coordination chemistry of the activation of [(triazacyclohexane)CrCl3] with [PhNMe2H][B(C6F5)4] and AlR3
Coordination chemistry of the activation of [(triazacyclohexane)CrCl3] with [PhNMe2H][B(C6F5)4] and AlR3
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DOI：
10.1016/s0022-328x(03)00634-x
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发表时间：
2003-10-07
影响因子：
2.3
通讯作者：
Kociok-Köhn, G
中科院分区：
文献类型：
--
作者：
Köhn, RD;Smith, D;Kociok-Köhn, G
N-取代的1，3，5-三氮杂环己烷与CrCl 3的配合物与[PhNMe 2 H][B（C6 F5）（4）]形成1：1加合物，在甲苯中的溶解度增加。（AlBu 3）-Bu 1的添加导致游离PhNMe 2和具有经由间氟原子弱配位至铬的[B（C6 F5）（4）]（-）的络合物。该络合物可以聚合和/或三聚烯烃类似于甲基铝氧烷活化的络合物。活性络合物的分解涉及三氮杂环己烷向铝的转移，导致[（三氮杂环己烷）（AlBu 2）-Bu 1][B（C6 F5）（4）]和[（芳烃）（2）Cr][B（C6 F5）（4）]。这些铬（I）络合物已通过X射线晶体学表征，并证明在催化过程中铬被还原为氧化态+I。(C)2003 Elsevier B. V.保留所有权利。
Complexes of N-substituted 1,3,5-triazacyclohexanes with CrCl3 form 1:1 adducts with [PhNMe2H][B(C6F5)(4)] with increased solubility in toluene. Addition of (AlBu3)-Bu-i leads to free PhNMe2 and a complex with [B(C6F5)(4)](-) weakly coordinated to chromium via a meta-fluorine atom. This complex can polymerise and/or trimerise olefins similar to methyl aluminoxane activated complexes. Decomposition of the active complex involves transfer of the triazacyclohexane to aluminium leading to [(triazacyclohexane) (AlBu2)-Bu-i][B(C6F5)(4)] and [(arene)(2)Cr][B(C6F5)(4)]. These chromium(I) complexes have been characterised by X-ray crystallography and prove that chromium is reduced to the oxidation state +I during the catalysis. (C) 2003 Elsevier B.V. All rights reserved.