Hydroamination of Carbodiimides, Isocyanates, and Isothiocyanates by Bis(phosphinoselenoic amide) Supported Titanium(IV) complex

Panda, Tarun K and Bhattacharjee, J and Das, S and Kottalanka, R K (2016) Hydroamination of Carbodiimides, Isocyanates, and Isothiocyanates by Bis(phosphinoselenoic amide) Supported Titanium(IV) complex. Dalton Transactions, 45. pp. 17824-17832. ISSN 1477-9226

Full text not available from this repository. (Request a copy)

Abstract

The hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by a bis(phosphinoselenoic amide) supported titanium(IV) complex as a precatalyst is reported here. The titanium(IV) complex [{Ph2P(Se)NCH2CH2NPPh2(Se)}Ti(NMe2)2] (1) was synthesised by the reaction of tetrakis-(dimethylamido)titanium(IV) [Ti(NMe2)4] with [{Ph2P(Se)NHCH2CH2NHPPh2(Se)}] in toluene at ambient temperature. Titanium complex 1 proved to be a competent pre-catalyst for the addition of an amine N–H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanates and phenylisothiocyanates in toluene solvents proceeding rapidly at room temperature with 5 mol% catalyst loadings to yield the corresponding urea and thio-urea derivatives up to 99%. However, ambient temperature was needed for hydroamination of 1,3-dicyclohexylcarbodiimide. The amine addition reactions with isocyanates showed first order kinetics with respect to catalyst 1 as well as substrates. The most plausible mechanism for the hydroamination reaction was established by isolating 1,1-dimethylphenyl urea as a side product.

[error in script]
IITH Creators:
IITH CreatorsORCiD
Panda, Tarun Khttp://orcid.org/0000-0003-0975-0118
Item Type: Article
Subjects: Chemistry
Divisions: Department of Chemistry
Depositing User: Team Library
Date Deposited: 24 Oct 2016 09:09
Last Modified: 07 Sep 2017 10:50
URI: http://raiith.iith.ac.in/id/eprint/2826
Publisher URL: https://doi.org/10.1039/C6DT03063G
OA policy: http://www.sherpa.ac.uk/romeo/issn/1477-9226/
Related URLs:

Actions (login required)

View Item View Item
Statistics for RAIITH ePrint 2826 Statistics for this ePrint Item