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Mitigating repulsions in close quarters: Copper tells us how!

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  • Inorganic & Physical Chemistry


Four copper(I) complexes of short bite ligands, bis(diphenylphosphino)amine (dppa) and bis(diphenylphosphino)isopropylamine (dppipa) were synthesized from appropriate precursors. All complexes were characterized by single crystal X-ray crystallography and spectroscopic techniques. In each of these complexes, two filled shell cations are forced into close proximity (\approx 2.7–2.8\AA). With no strong p acid ligands to siphon electron density from the filled d shell, the unavoidable repulsive $d^{10}-d^{10}$ interaction is mitigated when an unsymmetrical coordination environment around the copper atoms exists. The coordinatively saturated copper ion functions as a donor to the coordinatively unsaturated copper. A Cambridge Structural Database (CSD) search reveals the greater propensity of clusters with short contacts to adopt unsymmetrical coordination.

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