Cobalt( III ) complexes of 1,5,9-triamino-5-methyl-3,7-diazanonane, L 1 , a new quinquedentate polyamine ligand. Crystal structures of the chlorocobalt( III ) and µ-superoxo-dicobalt( III ) complexes of L 1

The polyamine 1,5,9-triamino-5-methyl-3,7-diazanonane (L1) co-ordinates as a quinquedentate ligand to cobalt(III). The monomers [Co(L1)X]2+(X = Cl–, NCS–, or NO2–) and the dimers [(CoL1)2O2]n+(n= 4 or 5) were prepared and characterized spectroscopically. The complex [Co(L1)Cl]Cl[ClO4] crystallizes in the monoclinic space group P21/c, a= 10.471(2), b= 11.878(3), c= 13.284(2)Å, and β= 97.70(1)°. The superoxo complex [(CoL1)2O2][ClO4]5·4H2O crystallizes in the triclinic space group P, a= 8.592(3), b= 9.792(3), c= 12.993(6)Å, α= 95.96(3), β= 97.70(1), and γ= 109.38(3)°. The cobalt–nitrogen bonds are unusually short in both structures, in the range 1.934–1.949(2)Å, and there is considerable strain in the molecules. The cobalt–chlorine bond in [Co(L1)Cl]Cl[ClO4] is also short [2.261(1)Å] and the rate of base hydrolysis of this bond is slow. The Raman-active O2 vibration in the peroxo-bridged dimer occurs ca. 40 cm–1 to lower wave number than for the deca-ammine analogue, indicative of a slightly longer O–O bond, whereas the O–O bond in the superoxo complex [1.294(14)Å] is shorter than that in the decaammine analogue.