将非三角磷配体插入到过渡金属-氢化物中：直接得到金属氢膦。
Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane.
机构信息
Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States.
出版信息
J Am Chem Soc. 2018 Jul 5;140(26):8114-8118. doi: 10.1021/jacs.8b05156. Epub 2018 Jun 25.
Abstract
The synthesis and reactivity of an NPN-chelating ligand containing a nontrigonal phosphorous triamide center (L1 = P(N( o-N(2-pyridyl)CH)) is reported. Metalation of L1 with RuCl(PPh) gives RuCl(PPh)(L1) (2). By contrast, metalation of L1 with RuHCl(CO)(PPh) yields RuCl(CO)(PPh)(L1) (3), a chelated 10-P-5 ruthenahydridophosphorane, via net insertion into the Ru-H bond. Hydride abstraction from 3 with PhCPF gives [RuCl(CO)(PPh)(L1)]PF (4); reaction of 4 with NaBH returns 3.
摘要
本文报道了一种含有非三角磷三酰胺中心的 NPN 螯合配体（L1 = P(N(邻-吡啶-2-基)CH)) 的合成与反应性。L1 与 RuCl(PPh)的金属化反应得到 RuCl(PPh)(L1)（2）。相比之下，L1 与 RuHCl(CO)(PPh)的金属化反应通过 Ru-H 键的净插入生成了螯合的 10-P-5 钌氢膦，得到 RuCl(CO)(PPh)(L1)（3）。从 3 中用 PhCPF 抽去氢得到 [RuCl(CO)(PPh)(L1)]PF（4）；4 与 NaBH 的反应将其返回 3。
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