A new diruthenium azido complex Ru2(chp)4N3 (1 , chp = 2-chloro-6-hydroxypyridinate) has been studied under photolytic conditions to investigate the chemical reactivity of the corresponding diruthenium nitride species Ru2(chp)4N towards intermolecular N-atom transfer to triphenylphosphine.  Photolysis of a dichloromethane solution of 1  with triphenylphosphine and an internal standard of PNPCl (PNPCl = bis(triphenylphosphoranylidene)ammonium chloride) at ? > 350 nm leads to a magenta solution.  Upon acidic workup, triphenylphosphinamine chloride is identified in a 63% yield and Ru2(chp)4Cl, the precursor to 1 , is regenerated and quantitatively identified, thereby creating a stoichiometric cycle for intermolecular N-atom transfer.  This cycle is the first example of a bimetallic nitride undergoing intermolecular reactivity and only the third cycle for complete N-atom transfer using a nitrido complex.  On-going studies include transforming this stoichiometric cycle into a catalytic one.

Stoichiometric cycle for complete N-atom transfer utilizing a new diruthenium nitrido complex

245th National Meeting (2013)

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