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Unusual Stabilities of 6,6'-Bis(aminomethyl)-2,2'-bipyridyl Chelates of Transition-metal Ions and Crystal Structures of the Ligand and its Copper(II) and Nickel(II) Complexes

DOI: 10.1039/DT9950001511

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1511 - 1518 (1995)

Update date:2022-07-30

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Authors:

Wang, ZhengWang, Zheng

Reibenspies, JosephReibenspies, Joseph

Motekaitis, Ramunas J.Motekaitis, Ramunas J.

Martell, Arthur E.Martell, Arthur E.

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Article abstract of DOI:10.1039/DT9950001511

An improved four-step synthesis of the tetradentate compound 6,6'-bis(aminomethyl)-2,2'-bipyridyl (badp) has been developed and the crystal structure of its dihydrochloride monohydrate determined: space group C2/c, a = 11.991(2), b = 5.703(1), c = 22.109(3) Angstroem, β = 97.17(1) deg and Z = 4.The complexes of copper(II) and nickel(II) with badp have also been synthesized and structurally characterized.The metal ion in Br2 is five-co-ordinated and the complex crystallizes in the monoclinic P21/c space group with a = 11.508(3), b = 9.584(3), c = 14.362(30 Angstroem, β = 107.93(2) deg and Z = 4.The complex Br contains six-co-ordinated Ni(II) and crystallizes in the monoclinic P21/c space group with a = 11.387(3), b = 9.417(2), c = 14.317(5) Angstroem, β = 106.21(2) deg and Z = 4.The stepwise stability constants of the 1 : 1 ligand to metal complexes of badp with divalent transition-metal ions have been determined in KCl as supporting electrolyte (0.100 mol dm-3) at 25.0 deg C: log KML = / for the Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes is 8.94, 10.16, 11.87, 15.05 and 10.02 respectively.Iron(II) and cobalt(II) also formed 2 : 1 complexes with badp.The unusually low stabilities of the transition-metal complexes are considered due to the low basicity of the ligand and to the unfavourable spacing of its donor groups as indicated by the structures of the complexes of Ni(II) and Cu(II).

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