Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane.

Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane.
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DOI:
10.1021/jacs.8b05156
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发表时间:
2018-07-05
影响因子:
15
通讯作者:
Radosevich AT
Radosevich AT
中科院分区:
化学1区
文献类型:
--
作者:
Tanushi A;Radosevich AT

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报道了一种含非三角磷三酰胺中心的NPN螯合配体(L1=P(N(o-N(2-吡啶基)C6H4)2))的合成和反应活性。L1与RuCl2(PPh3)3金属化合成RuCl2(PPh3)(L1)(2)。相反,L1与RuHCl(CO)(PPh_3)_3通过净插入Ru-H键生成RuCl(CO)(PPh_3)(L1H)(3)。用Ph3CPF6从3中提取氢化物得到[RuCl(CO)(PPh3)(L1)]PF6(4);4与NaBH4反应得到3。
The synthesis and reactivity of an NPN-chelating ligand containing a nontrigonal phosphorous triamide center (L1 = P(N(o-N(2-pyridyl)C6H4)2) is reported. Metalation of L1 with RuCl2(PPh3)3 gives RuCl2(PPh3)(L1) (2). By contrast, metalation of L1 with RuHCl(CO)(PPh3)3 yields RuCl(CO)(PPh3)(L1H) (3), a chelated 10-P-5 ruthenahydridophosphorane, via net insertion into the Ru–H bond. Hydride abstraction from 3 with Ph3CPF6 gives [RuCl(CO)(PPh3)(L1)]PF6 (4); reaction of 4 with NaBH4 returns 3.
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