Homo- and Heterodinuclear Ir and Rh Imine-functionalized Protic NHC Complexes: Synthetic, Structural Studies, and Tautomerization/Metallotropism Insights.
Homo- and Heterodinuclear Ir and Rh Imine-functionalized Protic NHC Complexes: Synthetic, Structural Studies, and Tautomerization/Metallotropism Insights.
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同核和异双核 Ir 和 Rh 亚胺功能化质子 NHC 配合物：合成、结构研究和互变异构/向金属性见解。
DOI：
10.1002/chem.201504030
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
P. Braunstein
中科院分区：
文献类型：
--
作者：
Fan He;M. Wesolek;A. Danopoulos;P. Braunstein
研究了亚胺官能化 Ir 和 Rh 咪唑配合物的潜在螯合亚氨基对通过互变异构/向金属序列形成官能化质子 N-杂环卡宾 (pNHC) 配合物的影响。用 TlPF6 从 [Ir(cod)Cl{C3 H3N2 (DippN=CMe)-κN3}] (1 a) (cod=1,5-环辛二烯，Dipp=2,6-二异丙基苯基)中提取氯化物，得到 [Ir(cod){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine) )}](+) [PF6 ](-) (3 a(+) [PF6 ](-))。推测了复合物 1 a 至 3 a(+) [PF6 ](-) 互变异构的合理机制，涉及 1 a 或 [Ir(cod){C3 H3 N2 (DippN=CMe)-κN3}2](+) [PF6 ](-) (6 a(+) [PF6 ](-)) 中的 C2-H 键激活。将 PR3 添加到络合物 3 a(+) [PF6 ](-) 中得到十八价电子络合物 [Ir(cod)(PR3){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (7 a(+) [PF6 ](-) (R=Ph) 和7 b(+) [PF6 ](-) (R=Me))。与 Ir 相比，在室温下从 [Rh(cod)Cl{C3H3N2 (DippN=CMe)-κN3}] (1 b) 提取氯化物得到 [Rh(cod){C3 H3N2 (DippN=CMe)-κN3}2](+) [PF6 ](-) (6 b(+) [PF6 ](-)) 和[Rh(鳕鱼){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (3 b(+) [PF6 ](-) )（轻微）；该反应在110℃的甲苯中仅产生后一种产物。还实现了唑环（C2 和 N3 原子）的双金属化：[Ir2 (cod)2 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (10) 和异双核配合物 [IrRh(cod)2 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (12) 得到充分表征。配合物 1 b, 3 b(+) [PF6 ](-) , 6 a(+) [PF6 ](-) , 7 a(+) [PF6 ](-), [Ir(cod){C3HN2 (DippN=CMe)(DippN=CH)(Me)-κ(2) (N3,Nimine )}](+) 的结构[PF6 ](-) (9(+) [PF6 ](-))、10⋅Et2O⋅甲苯、[Ir2(CO)4Cl{μ-C3H2N2(DippN=CMe)-κ(2)(C2,Nimine ),κN3}](11)和12⋅2 THF通过X射线衍射测定。
The influence of the potentially chelating imino group of imine-functionalized Ir and Rh imidazole complexes on the formation of functionalized protic N-heterocyclic carbene (pNHC) complexes by tautomerization/metallotropism sequences was investigated. Chloride abstraction in [Ir(cod)Cl{C3 H3N2 (DippN=CMe)-κN3}] (1 a) (cod=1,5-cyclooctadiene, Dipp=2,6-diisopropylphenyl) with TlPF6 gave [Ir(cod){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (3 a(+) [PF6 ](-)). Plausible mechanisms for the tautomerization of complex 1 a to 3 a(+) [PF6 ](-) involving C2-H bond activation either in 1 a or in [Ir(cod){C3 H3 N2 (DippN=CMe)-κN3}2](+) [PF6 ](-) (6 a(+) [PF6 ](-)) were postulated. Addition of PR3 to complex 3 a(+) [PF6 ](-) afforded the eighteen-valence-electron complexes [Ir(cod)(PR3){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (7 a(+) [PF6 ](-) (R=Ph) and 7 b(+) [PF6 ](-) (R=Me)). In contrast to Ir, chloride abstraction from [Rh(cod)Cl{C3H3N2 (DippN=CMe)-κN3}] (1 b) at room temperature afforded [Rh(cod){C3 H3N2 (DippN=CMe)-κN3}2](+) [PF6 ](-) (6 b(+) [PF6 ](-)) and [Rh(cod){C3 H3N2 (DippN=CMe)-κ(2) (C2,Nimine )}](+) [PF6 ](-) (3 b(+) [PF6 ](-) ) (minor); the reaction yielded exclusively the latter product in toluene at 110 °C. Double metallation of the azole ring (at both the C2 and the N3 atom) was also achieved: [Ir2 (cod)2 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (10) and the heterodinuclear complex [IrRh(cod)2 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (12) were fully characterized. The structures of complexes 1 b, 3 b(+) [PF6 ](-) , 6 a(+) [PF6 ](-) , 7 a(+) [PF6 ](-), [Ir(cod){C3HN2 (DippN=CMe)(DippN=CH)(Me)-κ(2) (N3,Nimine )}](+) [PF6 ](-) (9(+) [PF6 ](-)), 10⋅ Et2 O⋅toluene, [Ir2 (CO)4 Cl{μ-C3H2N2 (DippN=CMe)-κ(2) (C2,Nimine ),κN3}] (11), and 12⋅2 THF were determined by X-ray diffraction.
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影响因子：
15
作者：
Tan, KL;Bergman, RG;Ellman, JA
通讯作者：
Ellman, JA
影响因子：
16.6
作者：
Melaimi, Mohand;Soleilhavoup, Michele;Bertrand, Guy
通讯作者：
Bertrand, Guy
影响因子：
5.2
作者：
Tan, KL;Vasudevan, A;Souers, AJ
通讯作者：
Souers, AJ
影响因子：
15
作者：
Tan, KL;Bergman, RG;Ellman, JA
通讯作者：
Ellman, JA