Synthesis, Characterization and Theoretical Investigation on Thiazoline-Derived Palladium-Complexes-Catalyzed Denitrogenative Cross-Coupling of Aryl Halides with Arylhydrazines

Sudharsan, M and Thirumoorthy, K and Nethaji, M and Suresh, D (2019) Synthesis, Characterization and Theoretical Investigation on Thiazoline-Derived Palladium-Complexes-Catalyzed Denitrogenative Cross-Coupling of Aryl Halides with Arylhydrazines. In: ChemistrySelect, 4 (32). pp. 9253-9261.

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Abstract

Homo- and heteroleptic palladium(II) complexes of thiazoline derived ligand were synthesized and their catalytic application was reported. The reactions of [1-(C3H4NS)-2-OH-C6H4] (2) with PdCl2 and [(1-(CH3)2NCH2C6H4)PdCl]2 in 2:1 molar ratios afforded the homoleptic palladium complex, [Pd{κ1 2, κ1 2-N,O-(1-(C3H4NS)-2-O-C6H4)2}] (3) and the heteroleptic palladium complex [{κ1 2-N,O-(1-(C3H4NS)-2-O-C6H4)}Pd{(κ2 2-N,C-(1-(CH3)2NCH2C6H4)}] (4) respectively. Equimolar reactions of 2 with PdCl2 and 8-quinolinol or 2-methyl-8-quinolinol under reflux condition produced the heteroleptic palladium complexes [{κ1 2-N,O-(1-(C3H4NS)-2-O-C6H4)}Pd{(κ2 2-N,O-(8-O-C9H6-1-N)}] (5) or [{κ1 2-N,O-(1-(C3H4NS)-2-O-C6H4)}Pd{(κ2 2-N,O-(8-O-2-CH3-C9H5-1-N)}] (6) in good yields. The molecular structures of ligand 2 and palladium complexes 3–6 were confirmed through multinuclear NMR spectroscopic techniques and further the crystal structure for palladium complexes 3 and 4 were established. Under the optimized reaction condition, the heteroleptic palladium complex 4 display an excellent catalytic activity with a maximum turn over frequency of 49.5 h−1 for the conversion of bi-aryls from aryl halides and unactivated phenylhydrazine. The energies, activation barriers and transition state structures of reaction involved in the catalytic cycle were assessed by utilizing quantum chemical method to confirm Csp 2-Csp 2 bond formation reaction catalyzed by heteroleptic palladium complex 4.

Item Type:	Journal Article
Publication:	ChemistrySelect
Publisher:	Wiley-Blackwell
Additional Information:	The copyright for this article belongs to Wiley-Blackwell
Keywords:	Cross-coupling reactions; homo- and heteroleptic palladium(II); phenylhydrazine; theoretical investigation; thiazoline ligands
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	07 Jan 2023 05:49
Last Modified:	07 Jan 2023 05:49
URI:	https://eprints.iisc.ac.in/id/eprint/78861

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