Carbonylation of the ruthenium-methyl bond of Ru(Me)(I)(CO)2(i-Pr-N:CHCH:N-i-Pr) catalyzed by Ru(CO)4(PR3), ZnCl2, and H+
Carbonylation of the ruthenium-methyl bond of Ru(Me)(I)(CO)2(i-Pr-N:CHCH:N-i-Pr) catalyzed by Ru(CO)4(PR3), ZnCl2, and H+
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Ru(CO)4(PR3)、ZnCl2 和 H 催化 Ru(Me)(I)(CO)2(i-Pr-N:CHCH:N-i-Pr) 钌-甲基键的羰基化
DOI：
10.1021/om00059a047
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发表时间：
1992
期刊：
影响因子：
2.8
通讯作者：
A. Spek
中科院分区：
文献类型：
--
作者：
Marco J. A. Kraakman;B. D. Klerk;P. Lange;K. Vrieze;W. Smeets;A. Spek
1Bu-NC（10），PMe2Ph（11））。羰基化配合物10和11中的Ru-Me键的尝试没有成功。最后还发现H+和ZnCl_2也能促进3的Ru-Me键的羰基化反应。对配合物4和配合物8进行了单晶X-射线结构测定，并对它们的分子结构进行了讨论。显著的特征是4具有与3相似的构型;即，乙酰基是I的反式。发现8中的三氟磺酸根阴离子与钌中心配位，并与甲基反式配位。得到4（C_（12）H_（19）N_（20）RuI）为单斜晶系，空间群P_21/n，晶胞参数a= 8.556（1）A，B-18.510（2）A，c= 10.500（1）A，O = 94.90（1），V= 1656.7（3）A_3，Z= 4，对于I> 2.5o（I）的2565个反射和188个参数，最终R= 0.0435。8的晶体（C_（12）H_（19）F_3 N_（20）S_（20）RuS）为单斜晶系，空间群P_2x/c，晶胞参数a= 8.288（1）A，B= 25.839（2）A，c= 17.994（1）A，0= 100.47（1），V= 3789.1（6）A_3，Z= 8，对于I> 2.5 ≤ j（I）和500个参数的3917个反射，最终R= 0.0476。
‘Bu-NC (10), PMe2Ph (11)). Attempts to carbonylate the Ru-Me bond in complexes 10 and 11 were not successful. Finally it was shown that the carbonylation of the Ru-Me bond of 3 could also be promoted by H+ and ZnCl2. Single-crystal X-ray structure determinations of complexes 4 and 8 have been carried out, and their molecular structures are discussed. Salient features are that 4 has a configuration similar to that of 3; ie, the acetyl group is trans to I. The trifluorosulfonate anion in 8 is found to be^-coordinated to the ruthenium centerand trans to the methyl group. Crystals of 4 (C12H19N203RuI) are monoclinic, space group P21/n, with a= 8.556 (1) A, b-18.510 (2) A, c= 10.500 (1) A, 0= 94.90 (1), V= 1656.7 (3) A3, Z= 4, and final R= 0.0435 for 2565 reflections with I> 2.5 o (I) and 188 parameters. Crystals of 8 (C12H19F3N20sRuS) are monoclinic, space group P2x/c, with a= 8.288 (1) A, b= 25.839 (2) A, c= 17.994 (1) A, 0= 100.47 (1), V= 3789.1 (6) A3, Z= 8, and final R= 0.0476 for 3917 reflections with I> 2.5< j (I) and 500 parameters.