具有 NAD(+) / NADH 型配体的 Ru 配合物的光化学立体特异性氢化。

Photochemical stereospecific hydrogenation of a Ru complex with an NAD(+)/NADH-type ligand.

机构信息

Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787, Japan.

出版信息

Inorg Chem. 2009 Dec 21;48(24):11510-2. doi: 10.1021/ic901935u.

DOI:10.1021/ic901935u

PMID:19928751

Abstract

A polypyridylruthenium complex with an NAD(+)/NADH model ligand, Ru(bpy)(2)(pbn) [bpy = 2,2'-bipyridine; pbn = 2-(2-pyridyl)benzo[b]-1,5-naphthyridine] in a D(2)O/CH(3)CN/triethylamine solution, undergoes stereospecific hydrogenation to give Delta-(S)- and Lambda-(R)-Ru(bpy)(2)(pbnDD) [pbnDD = 5,10-dideutero-2-(2-pyridyl)benzo[b]-1,5-naphthyridine] upon visible-light irradiation. This result clearly indicates the pathway via the pi-stacked dimer of the deuterated one-electron-reduced species. The reduction of Ru(bpy)(2)(pbn) with Na(2)S(2)O(4) in D(2)O did not afford any stereospecific products. Furthermore, the more sterically crowded Ru complex, Ru(dmb)(2)(pbn) (dmb = 6,6'-dimethyl-2,2'-bipyridine), did not produce the corresponding pbnDD species upon irradiation.

摘要

一种具有 NAD(+) / NADH 模型配体的多吡啶钌配合物，Ru(bpy)(2)(pbn) [bpy = 2,2'-联吡啶；pbn = 2-(2-吡啶基)苯并[b]-1,5-萘啶]在 D(2)O/CH(3)CN/三乙胺溶液中，在可见光照射下会发生立体特异性氢化，生成 Delta-(S)-和 Lambda-(R)-Ru(bpy)(2)(pbnDD) [pbnDD = 5,10-氘代-2-(2-吡啶基)苯并[b]-1,5-萘啶]。这一结果清楚地表明了通过离域二聚体的单电子还原物种的途径。在 D(2)O 中用 Na(2)S(2)O(4)还原Ru(bpy)(2)(pbn)并没有得到任何立体特异性产物。此外，空间位阻更大的 Ru 配合物Ru(dmb)(2)(pbn) (dmb = 6,6'-二甲基-2,2'-联吡啶)在照射时也没有产生相应的 pbnDD 物种。