Polydentate 4‐Pyridyl‐terpyridine Containing Discrete Cobalt Phosphonate and Polymeric Cobalt Phosphate as Catalysts for Alcohol Oxidation

Abstract

Mononuclear discrete cobalt phosphonate [Co(pytpy)(tBuPO3H)2(H2O)]·H2O (1) and 1D zigzag polymeric cobalt phosphate [Co(pytpy)2(dipp)(MeOH)·2MeOH]n (2) were prepared from the reactions of tert‐butyl phosphonic acid (tBuPO3H2) and organic‐soluble 2,6‐diisopropylphenyl phosphate (dippH2) ligands with Co(OAc)2·4H2O in the presence of 4′‐pyridyl 2,2′:6′,2′′‐terpyridine in MeOH/CHCl3(1:1 v/v) solvent mixture at 25 °C. The new compounds were characterized by analytical, thermo‐analytical, and spectroscopic techniques. Further, the molecular structures were established by single‐crystal X‐ray diffraction studies. Mass spectrometry analysis reveal that both the compounds exist in the solution phase as dimers. Compound 1 was employed as homogeneous catalysts for alcohol oxidation reactions using tert‐butyl hydroperoxide (TBHP) as the oxidant.

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

“…From these, the Mn(II)‐containing system was found to catalyze the oxidation of primary and secondary alcohols with TBHP as oxidant (see Section 2.5.1); the Co(II) and Ni(II) counterparts were less efficient in terms of substrate conversion and selectivity. The self‐assembly of Co(OAc) 2 and ptpy in the presence of an organophosphor species yielded, in the solid state, either a mono‐nuclear complex (with tert‐butylphosphonate) or a coordination polymer (with 2,6‐diisopropylphenyl phosphate) . The former catalyzed the oxidation of alcohols to the corresponding carbonyl derivatives with very selectivity, i. e ., overoxidation of primary alcohols to carboxylic acids was hardly observed (acetonitrile, as solvent, offered the highest conversion and selectivity).…”

Solvothermal Synthesis and Characterizations of Two Isomerism Cobalt Phosphite‐Oxalates with Varying Dimensions Using the Same Template from in situ Reaction

“…Recently, the application of cobalt‐based crystalline and their derived materials is a hot topic in magnetic and electrochemistry field , . For instance, a chiral open‐framework cobalt phosphite [C 6 N 2 H 14 ][Co(HPO 3 ) 2 ] is a weak ferromagnet based on antiferromagnetic interaction and spin‐canting .…”