Mitigating repulsions in close quarters: Copper tells us how! |
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Authors: | Ritu Ahuja M NethajiAG Samuelson |
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Institution: | Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India |
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Abstract: | 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 (≈2.7–2.8 Å). With no strong π acid ligands to siphon electron density from the filled d shell, the unavoidable repulsive d10–d10 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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Keywords: | Copper Cambridge Structural Database (CSD) analysis Diphosphinoamine Metal&ndash metal interactions Short bite ligand Unsymmetrical coordination |
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