Synthesis and Photodriven Hydrogenation of Tungsten Nitride Complexes Prepared from Dinitrogen Cleavage

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High Resolution Image Download MS PowerPoint Slide Oxidation of the Chatt-type tungsten dinitrogen compound, trans -(depe) 2 W(N 2 ) 2 (depe = Et 2 PCH 2 CH 2 PEt 2 ), with [(η 5 -C 5 H 5 ) 2 Fe][BAr F 4 ] (BAr F 4 = B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ) resulted in isolation of [(depe) 2 WN][BAr F 4 ], a rare example of a tungsten(IV) nitride prepared from N 2 cleavage. A bimetallic μ-N 2 ditungsten intermediate supported by terminal N 2 ligands was identified, and irradiation with visible light promoted dinitrogen cleavage and formation of [(depe) 2 WN][BAr F 4 ]. Performing the analogous one-electron oxidation of the related tungsten dinitrogen compound, trans -(dppe) 2 W(N 2 ) 2 (dppe = Ph 2 PCH 2 CH 2 PPh 2 ), furnished the corresponding cationic, 17-electron tungsten dinitrogen complex, [(dppe) 2 W(N 2 ) 2 ][BAr F 4 ], that was characterized by X-ray diffraction and vibrational and EPR spectroscopies. The generation of [(dppe) 2 W(N)][BAr F 4 ] was observed in low yield from the in situ formed mixed N 2 -bridged compound, [(N 2 )(depe) 2 W(μ-N 2 )W(dppe) 2 (N 2 )][BAr F 4 ] 2, and was confirmed by independent synthesis using 1-azidoadamantane. Addition of ammonia or water to [(depe) 2 WN][BAr F 4 ] resulted in formation of the cationic imide and hydroxide complexes, [(depe) 2 W(NH)(X)][BAr F 4 ] (X = NH 2, OH). Irradiation of [(depe) 2 WN][BAr F 4 ] with 440 nm visible light in the presence of Ir(ppy) 3 (ppy = 2-phenylpyridine) under 4 atm of dihydrogen resulted in hydrogenation of the tungsten nitride to the cationic tungsten pentahydride, [(depe) 2 WH 5 ][BAr F 4 ], with the release of free ammonia in 21% yield, a rare example of ammonia generation from dinitrogen and dihydrogen from a well-defined tungsten nitride.

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