A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity. (16th August 2016)

• Record Type: Journal Article
• Authors: Schendzielorz, Florian S.; Finger, Markus; Volkmann, Christian; Würtele, Christian; Schneider, Sven
• Is Part Of: Angewandte Chemie. Volume 128:Number 38(2016)
• Page Start: 11589
• Page End: 11592
• Publication Date: 2016-08-16
• Subjects: Ammoniak -- Diwasserstoff -- Nitride -- Osmium -- Stickstofffixierung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201604917
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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.