Partl Gabriel Julian, Nussbaumer Felix, Schuh Walter, Kopacka Holger, Wurst Klaus, Peringer Paul
Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria.
Acta Crystallogr E Crystallogr Commun. 2019 Jan 1;75(Pt 1):75-80. doi: 10.1107/S2056989018017644.
The structure of [Ir{(4-Cl-CHN)C(dppm)-κ ,,}(dppm-κ ,')]Cl·1.5CHCl·0.5CH (CHClIrNP·1.5CHCl·0.5CH) (), dppm = bis-(di-phenyl-phosphino)methane {systematic name: [7-(4-chloro-phen-yl)-1,1,3,3-tetra-phenyl-5,6,7-tri-aza-κ -1,3λ-diphospha-κ -hepta-4,6-dien-4-yl][methyl-ene-bis(di-phenyl-phosphine)-κ ,']iridium(I) chloride-di-chloro-methane-toluene (2/3/1)}, resulting from the reaction of [IrClH{C(dppm)-κ ,,)(MeCN)]Cl () with 1-azido-4-chloro-benzene, shows a monocationic five-coordinate Ir complex with a distorted trigonal-bipyramidal geometry. In , the iridium centre is coordinated by the neutral triazeneyl-idene-phospho-rane (4-Cl-CHN)C(dppm) acting as a PCN pincer ligand, and a chelating dppm unit. The structure of the coordination compound [IrCl(CN)H(C(dppm)-κ ,,)]·CHCN, (CHClIrNP·CHCN) () [systematic name: chlorido-cyanidohydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,3λ,5λ,7-tetra-phospha-κ , -hept-3-en-4-yl)iridium(III) aceto-nitrile monosolvate], prepared from and KCN, reveals an octa-hedral Ir central atom with a meridional PCP pincer carbodi-phospho-rane (CDP) ligand; the chloride ligand is located to the central carbon of the CDP functionality while the hydrido and cyanido ligands are situated to each other. The chiral coordination compound [Ir(CN)((4-Cl-CHN)CH(CH(P(Ph)))-κ ,,)(dppm-κ ,')]·2CHOH, (CHClIrNP·2CHOH) () (systematic name: {4-[3-(4-chloro-phen-yl)triazenido-κ ]-1,1,3,3-tetra-phenyl-1,3λ-diphospha-κ -but-2-en-4-yl}cyanido[methyl-enebis(di-phenyl-phosphine)-κ ,']iridium(III) methanol disolvate), formed via prolonged reaction of 1-azido-4-chloro-benzene with , features a six-coordinate Ir central atom. The iridium centre is coordinated by the dianionic PCN pincer ligand [(4-Cl-CHN)CH(CH(P(Ph)))], a cyanido ligand to the central carbon of the PCN pincer ligand and a chelating dppm unit. Complex exhibits a 2:1 positional disorder of the Cl anion. The CHCl and CH solvent mol-ecules show occupational disorder, with the toluene mol-ecule exhibiting additional 1:1 positional disorder with some nearly overlying carbon atoms.
[Ir{(4 - Cl - CHN)C(dppm)-κ ,,}(dppm - κ ,')]Cl·1.5CHCl·0.5CH（CHClIrNP·1.5CHCl·0.5CH）（）的结构，dppm = 双（二苯基膦基）甲烷{系统名称：[7 - （4 - 氯苯基） - 1,1,3,3 - 四苯基 - 5,6,7 - 三氮杂 - κ - 1,3λ - 二磷杂 - κ - 庚 - 4,6 - 二烯 - 4 - 基][亚甲基双（二苯基膦） - κ ,']铱（I）氯化物 - 二氯甲烷 - 甲苯（2/3/1）}，由[IrClH{C(dppm)-κ ,,)(MeCN)]Cl（）与1 - 叠氮基 - 4 - 氯苯反应生成，显示出具有扭曲三角双锥几何构型的单核五配位铱配合物。在 中，铱中心由作为PCN钳形配体的中性三氮烯基亚甲基 - 膦环（4 - Cl - CHN）C(dppm)和螯合的dppm单元配位。配位化合物[IrCl(CN)H(C(dppm)-κ ,,)]·CHCN，（CHClIrNP·CHCN）（）[系统名称：氯代 - 氰基氢（1,1,3,3,5,5,7,7 - 八苯基 - 1,3λ,5λ,7 - 四磷杂 - κ , - 庚 - 3 - 烯 - 4 - 基）铱（III）乙腈单溶剂合物]，由 和KCN制备，揭示了一个八面体铱中心原子，带有一个经式PCP钳形碳二膦环（CDP）配体；氯配体位于CDP官能团中心碳的 位，而氢和氰基配体彼此位于 位。手性配位化合物[Ir(CN)((4 - Cl - CHN)CH(CH(P(Ph)))-κ ,,)(dppm - κ ,')]·2CHOH，（CHClIrNP·2CHOH）（）（系统名称：{4 - [3 - （4 - 氯苯基）三氮烯基 - κ ] - 1,1,3,3 - 四苯基 - 1,3λ - 二磷杂 - κ - 丁 - 2 - 烯 - 4 - 基}氰基[亚甲基双（二苯基膦） - κ ,']铱（III）甲醇二溶剂合物），通过1 - 叠氮基 - 4 - 氯苯与 的长时间反应形成，具有一个六配位铱中心原子。铱中心由双阴离子PCN钳形配体[(4 - Cl - CHN)CH(CH(P(Ph)))]、位于PCN钳形配体中心碳 位的氰基配体和螯合的dppm单元配位。配合物 表现出Cl阴离子的2:1位置无序。CHCl和CH溶剂分子表现出占位无序，甲苯分子表现出额外的1:1位置无序，一些碳原子几乎重叠。
