An unusually flexible expanded hexaamine cage and its CuII complexes: Variable coordination modes and incomplete encapsulation

Chang Jin Qin, Lloyd James, Jy D. Chartres, Leighton J. Alcock, Kimberley J. Davis, Anthony C. Willis, Alan M. Sargeson, Paul V. Bernhardt*, Stephen F. Ralph

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    19 Citations (Scopus)

    Abstract

    The bicyclic hexaamine "cage" ligand Me 8tricosaneN6 (1,5,5,9,13,13,20,20-octamethyl-3,7,11,15,18, 22-hexaazabicyclo[7.7.7]tricosane) is capable of encapsulating octahedral metal ions, yet its expanded cavity allows the complexed metal to adopt a variety of geometries comprising either hexadentate or pentadentate coordination of the ligand. When complexed to CuII the lability of the metal results in a dynamic equilibrium in solution between hexadentate- and pentadentate- coordinated complexes of Me8tricosaneN6. Both [Cu(Me 8tricosaneN6)](ClO4)2 (6-coordinate) and [Cu(Me8tricosaneN6)](S2O6) (5-coordinate) have been characterized structurally. In weak acid (pH 1) a singly protonated complex [Cu(HMe8tricosaneN6)] 3+ has been isolated that finds the ligand binding as a pentadentate with the uncoordinated amine being protonated. vis-NIR and electron paramagnetic resonance (EPR) spectroscopy show that the predominant solution structure of [Cu(Me8tricosaneN6)]2+ at neutral pH comprises a five-coordinate, square pyramidal complex. Cyclic voltammetry of the square pyramidal [Cu(Me8tricosaneN6)]2+ complex reveals a reversible CuII/I couple. All of these structural, spectroscopic, and electrochemical features contrast with the smaller cavity and well studied "sarcophagine" (sar, 3,6,10,13,16,19-hexaazabicyclo[6.6. 6]eicosane) CuII complexes which are invariably hexadentate coordinated in neutral solution and cannot stabilize a CuI form.

    Original languageEnglish
    Pages (from-to)9131-9140
    Number of pages10
    JournalInorganic Chemistry
    Volume50
    Issue number18
    DOIs
    Publication statusPublished - 19 Sept 2011

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