SYNTHESIS AND REACTIVITY OF THE IRIDIUM(I) MESITYL COMPLEX IR(CO)(MES)(DPPE) - OXIDATIVE ADDITION AND LIGAND ACTIVATION REACTIONS
SYNTHESIS AND REACTIVITY OF THE IRIDIUM(I) MESITYL COMPLEX IR(CO)(MES)(DPPE) - OXIDATIVE ADDITION AND LIGAND ACTIVATION REACTIONS
复制标题
DOI：
10.1021/ja00117a020
复制
发表时间：
1995-03-29
影响因子：
15
通讯作者：
EISENBERG, R
中科院分区：
文献类型：
--
作者：
CLEARY, BP;EISENBERG, R
通过 IrBr(CO)(dppe) 和异三甲苯基溴化镁的反应合成了配合物 Lr(CO)(mes)dppe (1)（mes = 1,3,5-三甲基苯基，dppe = 1,2-双（二苯基膦）乙烷）。配合物 1 在单斜空间群 P2(1)/n（编号 14）中结晶，Z = 4，a = 8.953(3) 埃，b = 22.752(6) 埃，c = 16.212(6) 埃，beta = 99.00(3) 度，并显示出方形平面性的轻微四面体畸变。当在乙烯下加热至 90°C 时，1 的苯溶液会发生不寻常的转变，通过邻甲基 C-H 活化形成五配位二甲基苄基络合物 Lr(eta(2)-C2H4)(CH2C6H3(CH3)2)(CO)(dppe) (2)。 2的X射线测定表明它在斜方空间群Pbca（No.61）中结晶，Z = 8，a = 19.113（8）埃，b = 16.243（9）埃，c = 23.174（7）埃。配合物 1 在 CO 作用下发生芳基迁移，形成二羰基加合物 Lr(Co)(2)(C(O)C6H2(CH3)(3))(dppe) (6)。配合物6的苯溶液加热后，形成反式-IrH(CO)(CH2C6H2(CH3)(2)C(O))(dPPe)(7)、顺式-IrH(CO)(CH2C6H2(CH3)(2)C(O))(dppe)(8)和6的平衡。配合物7和8是通过邻甲基C-H活化形成的。 8的晶体结构测定表明其结晶于单斜空间群P2(1)/n(No.14)，Z=4，a=10.701(3)埃，b=14.554(3)埃，20.760(6)埃，β=90.19(3)度。配合物 1 的溶液经历 HY (Y = SiHPh(2), H) 的立体定向氧化加成，分别形成 IrH(Y)(CO)(mes)(dppe) (9) (Y = SiHPh(2)) 和 10 (Y = H)。当1的苯溶液用I-2的苯溶液处理时，形成络合物LrI2(C(O)C6H2(CH3)(3))(dppe), 11。在 HCl 气体下，1 的 CD2Cl2 溶液很容易转化为 IrHCl2(CO)(dppe) (12) 和游离均三甲苯。
The complex Lr(CO)(mes)dppe (1) (mes = 1,3,5-trimethylphenyl, dppe = 1,2-bis(diphenylphosphino)ethane) has been synthesized from the reaction of IrBr(CO)(dppe) and mesitylmagnesium bromide. Complex 1 crystallizes in the monoclinic space group, P2(1)/n (No. 14), with Z = 4, a = 8.953(3) Angstrom, b = 22.752(6) Angstrom, c = 16.212(6) Angstrom, and beta = 99.00(3)degrees, and displays a slight tetrahedral distortion from square planarity. A benzene solution of 1 undergoes an unusual transformation when heated to 90 degrees C under ethylene to form the five-coordinate dimethylbenzyl complex Lr(eta(2)-C2H4)(CH2C6H3(CH3)2)(CO)(dppe) (2) via o-methyl C-H activation. An X-ray determination of 2 shows that it crystallizes in the orthorhombic space group, Pbca (No. 61), with Z = 8, a = 19.113(8) Angstrom, b = 16.243(9) Angstrom, c = 23.174(7) Angstrom. Complex 1 under CO undergoes aryl migration to form the dicarbonyl adduct Lr(Co)(2)(C(O)C6H2(CH3)(3))(dppe) (6). After a benzene solution of complex 6 is heated, an equilibrium of trans-IrH(CO)(CH2C6H2(CH3)(2)C(O))(dPPe) (7), cis-IrH(CO)(CH2C6H2(CH3)(2)C(O))(dppe) (8), and 6 is formed. Complexes 7 and 8 are formed by o-methyl C-H activation. A crystal structure determination of 8 shows that it crystallizes in the monoclinic space group P2(1)/n (No. 14), with Z = 4, a = 10.701(3) Angstrom, b = 14.554(3) Angstrom, 20.760(6) Angstrom, and beta = 90.19(3)degrees. Solutions of complex 1 undergo stereospecific oxidative additions of HY (Y = SiHPh(2), H) to form IrH(Y)(CO)(mes)(dppe) (9) (Y = SiHPh(2)) and 10 (Y = H), respectively. The complex LrI2(C(O)C6H2(CH3)(3))(dppe), 11, is formed when a benzene solution of 1 is treated with a benzene solution of I-2. Under HCl gas, a CD2Cl2 solution of 1 is readily converted to IrHCl2(CO)(dppe) (12) and free mesitylene.