Dataset for: "Does the configuration at metal matter in Noyori-Ikariya type asymmetric transfer hydrogenation catalysts?"

<b><i>Noyori-Ikariya type [(arene)RuCl(TsDPEN)] complexes are widely used C=O and C=N reduction catalysts which produce chiral alcohols and amines via a key ruthenium-hydride intermediate that determines the stereochemistry of the product. Whereas many details about the interactions of the pro-chiral substrate with the hydride complex, and the nature of the hydrogen transfer from the latter to the former have been investigated over the past 25 years, the role of the stereochemical configuration at the stereogenic ruthenium centre in the catalysis has not been elucidated so far. Using operando FlowNMR spectroscopy and Nuclear Overhauser Effect spectroscopy we show the existence of two diastereomeric hydride complexes under reaction conditions, assign their absolute configurations in solution, and monitor their interconversion during transfer hydrogenation catalysis. Configurational analysis and multi-functional DFT calculations show the λ-(R,R)S configured [(mesitylene)RuH(TsDPEN)] complex to be both thermodynamically and kinetically favoured over its λ-(R,R)R isomer with the opposite configuration at ruthenium. Computational analysis of both diastereomeric catalytic manifolds show the major λ-(R,R)S configured [(mesitylene)RuH(TsDPEN)] complex to dominate asymmetric ketone reduction catalysis, with the minor λ-(R,R)R [(mesitylene)RuH(TsDPEN)] stereoisomer being both less active and less enantioselective. These findings also hold true for a tethered catalyst derivative with a propyl linker between the arene and TsDPEN ligands, and thus show enantioselective transfer hydrogenation catalysis with Noyori-Ikariya complexes to proceed via a lock-and-key mechanism.</i></b><br>

野依良治-伊卡里亚（Noyori-Ikariya）型[(芳烃)RuCl(TsDPEN)]配合物是一类应用广泛的C=O与C=N还原催化剂，其通过关键的钌氢中间体生成手性醇与手性胺，该中间体直接决定产物的立体化学构型。尽管在过去25年间，学界已针对前手性底物与该氢合配合物的相互作用，以及氢从氢合配合物向底物转移的本质开展了大量研究，但催化过程中手性钌中心的立体化学构型所发挥的作用至今仍未被阐明。本研究借助原位流动核磁共振（operando FlowNMR）波谱技术与核奥弗豪泽效应（Nuclear Overhauser Effect, NOE）波谱技术，观测到反应条件下存在两种非对映异构的氢合配合物，确定了它们在溶液中的绝对构型，并实时监测了转移加氢催化过程中二者的相互转化。构型分析与多功能密度泛函理论（DFT）计算结果表明，λ-(R,R)S构型的[(均三甲苯)RuH(TsDPEN)]配合物，相较于钌中心构型相反的λ-(R,R)R异构体，在热力学与动力学上均更具优势。对两条非对映异构催化循环路径的计算分析显示，占主导地位的λ-(R,R)S构型[(均三甲苯)RuH(TsDPEN)]配合物主导了不对称酮还原催化过程；而占比极少的λ-(R,R)R [(均三甲苯)RuH(TsDPEN)]立体异构体不仅催化活性更低，对映选择性也更差。上述结论同样适用于一种在芳烃配体与TsDPEN配体之间连接丙基桥的锚定型催化剂衍生物，由此证实，野依良治-伊卡里亚型配合物介导的对映选择性转移加氢催化过程遵循锁钥作用机制。