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

摘要

The complexation of di-(2-pyridylmethyl)amine to RuHCl(PPh _3)_3 affords the salt [RuH{κ~3N-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~3C~(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~3N-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.