From amine to ruthenaziridine to azaallyl: unusual transformation of di-(2-pyridylmethyl)amine on ruthenium.

The complexation of di-(2-pyridylmethyl)amine to RuHCl(PPh(3))(3) affords the salt [RuH{κ(3)N-fac-1,3-di-(2-pyridylmethyl)amine}(PPh(3))(2)]Cl. Reaction with potassium tert-butoxide at room temperature yields the unusual ruthenaziridine complex RuH{κ(3)C(alk)NN(py)-1,3-di-(2-pyridylmethyl)amine}(PPh(3))(2), where the central nitrogen atom, adjacent alkyl carbon, and pyridine arm coordinate to the metal, leaving the second pyridine arm uncoordinated. Surprisingly, heating of this ruthenaziridine complex with concomitant H(2) formation affords the ruthenium azaallyl complex RuH(κ(3)N-1,3-di-(2-pyridyl)-2-azaallyl)(PPh(3))(2). This is a rare example of a 4d metal complex containing the azaallyl ligand. X-Ray crystal structures and NMR characterization of all three compounds are presented herein.