A Dicyanomethyl Radical Conjugated with a Pyridylamino Group: Combining Radical-based Dynamic Covalent Chemistry and Coordination Chemistry |
| |
Authors: | Hiroki Hasegawa Daisuke Sakamaki Hideki Fujiwara |
| |
Institution: | Department of Chemistry, Graduate School of Science, Osaka Metropolitan University Naka-ku, Sakai-shi, Osaka, 599-8531 Japan |
| |
Abstract: | In this work, we aimed to develop a dicyanomethyl radical that undergoes both reversible C−C bond formation/dissociation and metal-ligand coordination reactions to combine dynamic covalent chemistry (DCC) based on organic radicals with coordination chemistry. We have previously reported a dicyanomethyl radical conjugated with a triphenylamine ( 1 ⋅) that exhibits a monomer/dimer equilibrium between the σ-bonded dimer ( 12 ). We designed and synthesized a novel dicyanomethyl radical with a pyridyl group as a coordination point ( 2 ⋅) by replacing the phenyl group of 1 ⋅ with a 3-pyridyl group. We showed that 2 ⋅ is also in an equilibrium with the σ-bonded dimer ( 22 ) in solution and has suitable thermodynamic parameters for application in DCC. 22 coordinates to PdCl2 in a 2 : 2 ratio to selectively form a metallamacrocycle ( 22 )2(PdCl2)2, and its structure was clarified by single crystal X-ray analysis. Variable-temperature NMR, ESR, and electronic absorption measurements revealed that ( 22 )2(PdCl2)2 also undergoes the reversible C−C bond formation/dissociation reaction. Ligand-exchange experiment showed that 22 was liberated from ( 22 )2(PdCl2)2 by the addition of another ligand with a higher affinity for PdII. This work demonstrated that DCC based on dicyanomethyl radicals works orthogonally to metal-ligand coordination reactions. |
| |
Keywords: | Coordination Chemistry Dynamic Covalent Chemistry Macrocyclic Complex Organic Radical Self-Assembly |
|
|