title: A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity.
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.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 1, 37077, Göttingen, Germany.
authors.forename: Florian S
authors.initials: FS
authors.lastname: Schendzielorz
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 1, 37077, Göttingen, Germany.
authors.forename: Markus
authors.initials: M
authors.lastname: Finger
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 1, 37077, Göttingen, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Volkmann
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 1, 37077, Göttingen, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Würtele
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 1, 37077, Göttingen, Germany. sven.schneider@chemie.uni-goettingen.de.
authors.forename: Sven
authors.identifier: 0000-0002-8432-7830
authors.initials: S
authors.lastname: Schneider
keywords: ammonia; dihydrogen; nitride; nitrogen fixation; osmium