A rare methyleneimine complex of ruthenium(II), cis‐[Ru(NHCH2)(NCCH3)(bpy)2]2+ (see structure), was obtained from the reaction of cis‐[Ru(N3)2(bpy)2]⋅H2O (bpy=2,2′‐bipyridine) with CH3I in CH3CN at room temperature in the dark. The reaction of such azido complexes will be useful in the synthesis of nitrogen‐containing ligands.
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