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Dinitrogen‐Molybdenum Complex Induces Dinitrogen Cleavage by One‐Electron Oxidation
71
Citations
61
References
2019
Year
Reported here is the N<sub>2</sub> cleavage of a one-electron oxidation reaction using trans-[Mo(depe)<sub>2</sub> (N<sub>2</sub> )<sub>2</sub> ] (1) (depe=Et<sub>2</sub> PCH<sub>2</sub> CH<sub>2</sub> PEt<sub>2</sub> ), which is a classical molybdenum(0)-dinitrogen complex supported by two bidentate phosphine ligands. The molybdenum(IV) terminal nitride complex [Mo(depe)<sub>2</sub> N][BArf<sub>4</sub> ] (2) (BArf<sub>4</sub> =B(3,5-(CF<sub>3</sub> )<sub>2</sub> C<sub>6</sub> H<sub>3</sub> )<sub>4</sub> ) is synthesized by the one-electron oxidation of 1 upon addition of a mild oxidant, [Cp<sub>2</sub> Fe][BArf<sub>4</sub> ] (Cp=C<sub>5</sub> H<sub>5</sub> ), and proceeds by N<sub>2</sub> cleavage from a Mo<sup>II</sup> -N=N-Mo<sup>II</sup> structure. In addition, the electrochemical oxidation reaction for 1 also cleaved the N<sub>2</sub> ligand to give 2. The dimeric Mo complex with a bridging N<sub>2</sub> is detected by in situ resonance Raman and in situ UV-vis spectroscopies during the electrochemical oxidation reaction for 1. Density-functional theory (DFT) calculations reveal that the unstable monomeric oxidized Mo<sup>I</sup> species is converted into 2 via the dimeric structure involving a zigzag transition state.
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