2-Picolylamino(diphenylphosphinoselenoic)amide supported zinc complexes: Efficient catalyst for insertion of N–H bond into carbodiimides, isocyanates, and isothiocyanate

Harinath, Adimulam and Bano, Kulsum and Ahmed, Shakil and Panda, Tarun K (2017) 2-Picolylamino(diphenylphosphinoselenoic)amide supported zinc complexes: Efficient catalyst for insertion of N–H bond into carbodiimides, isocyanates, and isothiocyanate. Phosphorus, Sulfur, and Silicon and the Related Elements. pp. 1-10. ISSN 1042-6507

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Abstract

We report here the hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by zinc complexes supported by the ligand 2-picolylamino-(diphenylphosphinoselenoic)amide [{(Ph2P-(˭Se)}2NCH2(C5H4N)] (1). A series of zinc complexes [κ2-{(Ph2P-(˭Se)}2NCH2(C5H4N)ZnX2] [(X˭Cl (2), Br (3a), I (4)] were prepared from ligand 1 and the corresponding zinc dihalide in a 1:1 molar ratio at 60°C in a chloroform solvent. The reaction of ligand 1 and ZnBr2 in methanol yielded another zinc complex [κ2-{(Ph2P-(˭Se)}2NCH2(C5H4N)ZnBr2(CH3OH)] (3b). The molecular structures of compounds 3a, 3b, and 4 were established through single-crystal X-ray diffraction analyses. The solid-state structures of all the complexes revealed a κ2- chelation through pyridine nitrogen and selenium atoms of ligand 1 to the zinc ion. Complex 2 proved to be a competent pre-catalyst for the addition of the amine N–H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanate and phenylisothiocyanate in toluene solvents, which proceeded rapidly at room temperature with 5 mol% catalyst loading to yield (up to 99%) the corresponding derivatives of urea and thio-urea. However, a temperature of 90°C was needed for the hydroamination of N,N′ dicyclohexylcarbodiimide. We also report the most plausible mechanism of the hydroamination reaction.

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IITH Creators:
IITH CreatorsORCiD
Panda, Tarun Khttp://orcid.org/0000-0003-0975-0118
Item Type: Article
Uncontrolled Keywords: P-N Ligands, Selenium, Sulfur, Carbodiimides, Isocyanate, Isothiocyanate, Zinc
Subjects: Chemistry > Organic chemistry
Divisions: Department of Chemistry
Depositing User: Team Library
Date Deposited: 07 Sep 2017 10:22
Last Modified: 07 Sep 2017 10:22
URI: http://raiithold.iith.ac.in/id/eprint/3529
Publisher URL: http://doi.org/10.1080/10426507.2017.1370590
OA policy: http://www.sherpa.ac.uk/romeo/issn/1042-6507/
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