A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity |
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Authors: | M?Sc Florian S Schendzielorz Dr Markus Finger M?Sc Christian Volkmann Dr Christian Würtele Prof?Dr Sven Schneider |
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Institution: | Institut für Anorganische Chemie, Georg-August-Universit?t, G?ttingen, Germany |
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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(CH2CH2P(tBu)2)2) is reported upon reversible deprotonation of osmium(VI) hydride Os(N)H(PNP)]+. The OsIV complex shows ambiphilic nitride reactivity with SiMe3Br 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. |
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Keywords: | ammonia dihydrogen nitride nitrogen fixation osmium |
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