A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity.
A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity.
复制标题
DOI：
10.1002/anie.201604917
复制
发表时间：
2016-09
影响因子：
--
通讯作者：
Florian Schendzielorz;Markus Finger;Christian Volkmann;Christian Würtele;S. Schneider
中科院分区：
文献类型：
--
作者：
Florian Schendzielorz;Markus Finger;Christian Volkmann;Christian Würtele;S. Schneider
在固氮方案中，讨论了低价氮化锶作为中间体的问题。然而，目前尚不清楚导致可分离例子的合理合成路线。本文报道了四方平面氮化锶[Osn(PnP)](PnP=N(CH2CH2P(Tbu)2)2)的合成。Os(IV)络合物分别与SiMe3BR和PMe3具有双亲氮化反应活性。重要的是，与氢的氢解得到了氨和聚氢化物[OsH4(HPNP)]，产率为80%。因此，我们的结果直接证明了在碱性条件下，低价氮化锶和异解氢活化在合成氨反应中的作用。
Low-valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square-planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH2 CH2 P(tBu)2 )2 ) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)](+) . The Os(IV) complex shows ambiphilic nitride reactivity with SiMe3 Br and PMe3 , respectively. Importantly, the hydrogenolysis with H2 gives ammonia and the polyhydride complex [OsH4 (HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low-valent osmium nitrides and of heterolytic H2 activation for ammonia synthesis with H2 under basic conditions.