Abstract

ABSTRACT This paper portrays the solution-phase dynamics as copper(II) and ethylenediamine explore a multitude of different complexes. The data from five spectrophotometric titrations were globally analysed, evidencing four predominant species ([Cu]2+, [Cu(en-N,N’)]2+, [Cu(en-N,N’)2]2+, [Cu(en-N)4]2+) along with their molar absorptivity curves and associative binding constants. The data also seem to support a fifth species, [Cu2(µ-en-N,N’)]4+, in which ethylenediamine bridges two Cu(II) centres. The thermodynamic stability of all five species is corroborated by ab initio computational calculations. The potential existence of [Cu(en-N)4]2+ highlights the suprachelate effect – going beyond the chelate effect – where multidenticity is overtaken by monodenticity. Such dangling multidentate ligands are available to bind to additional metal centres and thus build towards self-assembling supramolecules.

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