Macrocyclic bis-diphosphenes demonstrating bimetallic exo - and endo -cyclic binding modes.

Macrocyclic bis-diphosphenes, formally heavier derivatives of macrocyclic azobenzenes, are accessed for the first time. These are synthesised in a reproducible fashion, through the nickel-mediated homocoupling of xanthene-derived NHC-stabilised bis-phosphinidene units. This gives direct access to target macrocyclic bis-diphosphenes 2, featuring exo -cyclic coordinated Ni 0 fragments. The endo -cyclic binding mode in 3 is realised by NHC-abstraction using CuCl, so demonstrating two homometallic binding modes for this system. Additionally, reaction with CuCl in acetonitrile yields small amounts of a tetra-metallic Ni II /Cu I complex, which establishes simultaneous exo - and endo -cyclic metal binding. Fluctional solution state behavior in these systems is explored through variable temperature NMR spectroscopy, in addition to computational bonding analyses, giving the first insights into this novel class of compounds.