Dinuclear tethered pyridine, diimine complexes

Abstract

The regioselective borylation of pyridine precursors, followed by Suzuki coupling with dihalogenated linker molecules, provides access to tethered ligands. Complexation with MX2 salts results in the formation of dinuclear metal compounds. Syntheses and crystal structures are reported along with a discussion on the rigidity/flexibility of these new ligand systems.

Synthesis and reactivity of dinuclear copper(i) pyridine diimine complexes

“…The naphthyl bridged pyridine diimine ligand 2 was synthesized by the condensation of neo -pentylamine with the ketone precursor 1 in 74% yield (Scheme 1). 27 Due to the neo -pentyl substituents ligand 2 displays a good solubility in aliphatic solvents, e.g. n -pentane and n -hexane.…”

“…Deuterated THF was dried over sodium benzophenone ketyl and deuterated dichloromethane was dried over calcium hydride and stored under nitrogen. The ligand precursor 1 27 and Na[BAr F 4 ] 39 were synthesized following published procedures. All other chemicals were purchased from commercial sources and used as received.…”

“…Herein, we report the synthesis of a new PDI ligand with two binding manifolds based on a previously established ligand synthesis route by us. 27 Additionally, the synthesis of a cationic dicopper( i ) complex with a small dichloridocuprate( i ) and a large anion tetrakis(3,5-bis-(trifluoromethyl)-phenyl)borate ([BAr F 4 ] − ) is described. Furthermore, the reactivity of the cationic dicopper( i ) complex towards CO is investigated.…”

Template-Free Synthesis of a Macrocyclic Bis(pyridine-dienamine) Proligand and Metal Complexes of Its Bis(pyridine-diimine) and Bis(pyridine-dienamido) Forms

“…Two limiting conformations for these units, (s- cis ) 2 and (s- trans ) 2 , are shown in Scheme . While the (s- cis ) 2 conformation is present in (PDI)­M complexes, free PDK, PIK, and PDI ligands normally adopt the (s- trans ) 2 conformation because in this conformation the CX (X = O or NR)/pyridine lone-pair repulsion that is present in the (s- cis ) 2 conformation is relieved. ,− The final intermediate in the formation of a bis-PDI macrocycle in a PDK/dianiline condensation reaction is a species that has one PIK moiety, one PDI unit, and one amine group (Scheme ). In the ground-state 2­(s- trans ) 2 conformer of this intermediate, the distance between the reactive ketone and amine groups is maximized and the formation of the condensation polymer is favored.…”

1,8‐Diarylnaphthalenes: Synthesis, Properties, and Applications

“…[126][127][128] The Suzuki coupling of peri-diiodide 7 with boronate 207 gave the dipyridylnaphthalene derivative 188, which was further converted into the polydentate pyridine-diimine (PDI) ligand 209 (Scheme 65). [129] Based on PDI ligand, dinuclear transition metal complexes were synthesized. The latter were used as catalysts for some industrially important reactions (e.g., olefin polymerization).…”