Synthesis
and Reactivity of a Transient, Terminal
Nitrido Complex of Rhodium
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Abstract
Irradiation
of rhodium(II) azido complex [Rh(N<sub>3</sub>){N(CHCHP<i>t</i>Bu<sub>2</sub>)<sub>2</sub>}] allowed for the spectroscopic
characterization of the first reported rhodium complex with a terminal
nitrido ligand. DFT computations reveal that the unpaired electron
of rhodium(IV) nitride complex [Rh(N){N(CHCHP<i>t</i>Bu<sub>2</sub>)<sub>2</sub>}] is located in an antibonding Rh–N π*
bond involving the nitrido moiety, thus resulting in predominant N-radical
character, in turn providing a rationale for its transient nature
and observed nitride coupling to dinitrogen
