Axial Chirality and Supramolecular Interactions:  The Case of [(κ²-P,P-{PPh₂NMe}₂CO)Cu^ICl]₂

Abstract

The title compound [(kappa2-P,P-[PPh(2)NMe}2CO)Cu(I)Cl]2 (4) is readily formed by the reaction between (PPh2NMe)2CO and copper(I) chloride. Compound 4 forms a two-dimensional supramolecular network of Cu2Cl2-centered dimers that are linked by pi-pi interaction between the phenyl substituents on phosphorus in the solid state. Because of the nature of these pi-pi interactions, only one of the three possible enantiomers, the meso form, can be observed in the crystals.

Tryptophan π‐Electron System Capping a Copper(I) Binding Site—A New Organometallic Bonding Mode in Proteins

“…Copper(I) is a d 10 closed‐shell metal ion and isoelectronic to nickel(0). Like Ni 0 , Cu I prefers a tetrahedral coordination geometry, although tricoordinate compounds are well known 22. 23 It is easily oxidised to Cu II due to Jahn–Teller stabilisation in the ensuing d 9 metal ion.…”

“…Solid‐state structures of small‐model complexes are not always preserved in solution,22, 23 but an elaborate 2D 1 H, 13 C NMR study of the model Cu I complex with a hemilabile naphthyl ligand proved invaluable in showing that the solid‐state structure is essentially preserved in solution. The η 2 ‐naphthyl ligand indeed shows dynamic behaviour on the NMR timescale and binds with 12–13 kcal mol −1 29.…”