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Detection of an Iridium–Dihydrogen Complex: A Proposed Intermediate in Ionic Hydrogenation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-01 , DOI: 10.1021/jacs.7b06480 Jonathan M. Goldberg 1 , Karen I. Goldberg 1 , D. Michael Heinekey 1 , Samantha A. Burgess 2 , David B. Lao 2 , John C. Linehan 2
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-01 , DOI: 10.1021/jacs.7b06480 Jonathan M. Goldberg 1 , Karen I. Goldberg 1 , D. Michael Heinekey 1 , Samantha A. Burgess 2 , David B. Lao 2 , John C. Linehan 2
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Addition of high pressures of H2 to five-coordinate [(tBu)4(POCOP)Ir(CO)(H)]OTf [(tBu)4(POCOP) = κ3-C6H3-2,6-(OP(tBu)2)2] complexes results in observation of two new iridium-dihydrogen complexes. If the aryl moiety of the POCOP ligand is substituted with an electron withdrawing protonated dimethylamino group at the para position, hydrogen coordination is enhanced. Five-coordinate Ir-H complexes generated by addition of triflic acid to (tBu)4(POCOP)Ir(CO) species show an Ir-H 1H NMR chemical shift dependence on the number of equivalents of acid present. It is proposed that excess triflic acid in solution facilitates triflate dissociation from iridium, resulting in unsaturated five-coordinate Ir-H complexes. The five-coordinate iridium-hydride complexes were found to catalyze H/D exchange between H2 and CD3OD. The existence of the dihydrogen complexes, as well as isotope exchange reactions, provide evidence for proposed ionic hydrogenation intermediates for glycerol deoxygenation.
中文翻译：
铱-二氢配合物的检测：一种提议的离子氢化中间体
将高压 H2 添加到五坐标 [(tBu)4(POCOP)Ir(CO)(H)]OTf [(tBu)4(POCOP) = κ3-C6H3-2,6-(OP(tBu)2 )2] 配合物导致观察到两种新的铱-二氢配合物。如果 POCOP 配体的芳基部分在对位被吸电子质子化二甲氨基取代，则氢配位增强。通过将三氟甲磺酸加入 (tBu)4(POCOP)Ir(CO) 物种生成的五配位 Ir-H 配合物显示出 Ir-H 1H NMR 化学位移依赖于当前酸的当量数。建议溶液中过量的三氟甲磺酸促进三氟甲磺酸从铱中解离，从而产生不饱和的五配位 Ir-H 配合物。发现五配位铱-氢化物配合物可催化 H2 和 CD3OD 之间的 H/D 交换。
更新日期：2017-09-01
中文翻译：
铱-二氢配合物的检测：一种提议的离子氢化中间体
将高压 H2 添加到五坐标 [(tBu)4(POCOP)Ir(CO)(H)]OTf [(tBu)4(POCOP) = κ3-C6H3-2,6-(OP(tBu)2 )2] 配合物导致观察到两种新的铱-二氢配合物。如果 POCOP 配体的芳基部分在对位被吸电子质子化二甲氨基取代，则氢配位增强。通过将三氟甲磺酸加入 (tBu)4(POCOP)Ir(CO) 物种生成的五配位 Ir-H 配合物显示出 Ir-H 1H NMR 化学位移依赖于当前酸的当量数。建议溶液中过量的三氟甲磺酸促进三氟甲磺酸从铱中解离，从而产生不饱和的五配位 Ir-H 配合物。发现五配位铱-氢化物配合物可催化 H2 和 CD3OD 之间的 H/D 交换。
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