Premium
Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel
Author(s) -
Kumar Amit,
Lionetti Davide,
Day Victor W.,
Blakemore James D.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704006
Subject(s) - chemistry , lewis acids and bases , bimetallic strip , crown ether , nickel , redox , macrocyclic ligand , solvent , ligand (biochemistry) , electrochemistry , polymer chemistry , ether , inorganic chemistry , combinatorial chemistry , organic chemistry , metal , ion , catalysis , electrode , biochemistry , receptor
Assembly of heterobimetallic complexes is synthetically challenging due to the propensity of ditopic ligands to bind metals unselectively. Here, we employ a novel divergent approach for selective preparation of a variety of bimetallic complexes within a ditopic macrocyclic ligand platform. In our approach, nickel is readily coordinated to a Schiff base cavity, and then a range of redox‐inactive cations (M=Na + , Ca 2+ , Nd 3+ , and Y 3+ ) are installed in a pendant crown‐ether‐like site. This modular strategy allows access to complexes with the highly Lewis acidic trivalent cations Nd 3+ and Y 3+ , a class of compounds that were previously inaccessible. Spectroscopic and electrochemical studies reveal wide variations in properties that are governed most strongly by the trivalent cations. Exposure to dimethylformamide drives loss of Nd 3+ and Y 3+ from the pendant crown‐ether site, suggesting solvent effects must be carefully considered in future applications involving use of highly Lewis acidic metals.