Hydrogenation of CO2, carbonyl and imine substrates catalyzed by IrH3((PNP)-P-Ph-P-H)] complex

Ramaraj, Ayyappan and Nethaji, Munirathinam and Jagirdar, Balaji R (2019) Hydrogenation of CO2, carbonyl and imine substrates catalyzed by IrH3((PNP)-P-Ph-P-H)] complex. In: JOURNAL OF ORGANOMETALLIC CHEMISTRY, 883 . pp. 25-34.

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Abstract

A series of iridium and rhodium complexes M(COD)((PNP)-P-Ph-P-H)]Cl {M = Ir (1), Rh (2)}, MH2Cl((PNP)-P-Ph-P-H)] {M = Ir (3), Rh (4)} and IrH3((PNP)-P-Ph-P-H)] (6) supported by pincer ligand HeN(CH2CH2PPh2)(2) {(PNP)-P-Ph-P-H} have been synthesized and characterized. All complexes were isolated in good yields. The iridium trihydride complex IrH3((PNP)-P-Ph-P-H)] (6) was found to be an active catalyst for the hydrogenation of CO2 in 1 M aqueous KOH solution. It also acts as a catalyst for the base-free hydrogenation of carbonyl and imine substrates in MeOH. Under similar hydrogenation conditions, 2-cyclohexen-1-one undergoes solvent assisted tandem Michael addition-reduction mediated by bifunctional Lewis-acid-catalyst IrH3((PNP)-P-Ph-P-H)] in ROH (R = Me, Et) at room temperature. The complexes 1, 3, 4, and 6 were characterized by X-ray crystallography. Extensive hydrogen bonding interactions N-H center dot center dot center dot H-Ir (2.15 angstrom), N-H center dot center dot center dot center dot Cl (2.370 angstrom) were noted in the crystal structures of these complexes. (C) 2018 Elsevier B.V. All rights reserved.

Item Type:	Journal Article
Publication:	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Publisher:	ELSEVIER SCIENCE SA
Additional Information:	Copyright of this article belongs to ELSEVIER SCIENCE SA
Keywords:	Pincer ligand; Iridium complexes; NMR spectroscopy; CO2 activation; Hydrogenation; Catalysis
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	22 Feb 2019 05:30
Last Modified:	22 Feb 2019 05:30
URI:	http://eprints.iisc.ac.in/id/eprint/61802

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