Premium
A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity
Author(s) -
Schendzielorz Florian S.,
Finger Markus,
Volkmann Christian,
Würtele Christian,
Schneider Sven
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201604917
Subject(s) - osmium , reactivity (psychology) , deprotonation , nitride , chemistry , ammonia , ruthenium , organic chemistry , catalysis , medicine , ion , alternative medicine , pathology , layer (electronics)
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(CH 2 CH 2 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 SiMe 3 Br and PMe 3 , respectively. Importantly, the hydrogenolysis with H 2 gives ammonia and the polyhydride complex [OsH 4 (HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low‐valent osmium nitrides and of heterolytic H 2 activation for ammonia synthesis with H 2 under basic conditions.