P,N-type phosphaalkene-based Ir(i) complexes: synthesis, coordination chemistry, and catalytic applications

Gupta, Priyanka, Drexler, Hans-Joachim, Wingad, Richard, Wass, Duncan ORCID: https://orcid.org/0000-0002-0356-7067, Baráth, Eszter, Beweries, Torsten and Hering-Junghans, Christian 2023. P,N-type phosphaalkene-based Ir(i) complexes: synthesis, coordination chemistry, and catalytic applications. Inorganic Chemistry Frontiers 10 (8) , pp. 2285-2293. 10.1039/D3QI00142C

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Abstract

Phosphaalkenes are an emerging class of ligands with unique electronic properties that can be regarded as tuneable variants of the ubiquitous CO ligand. Our group has recently reported the synthesis of the P,N-type phosphaalkene ligand quin-CH[double bond, length as m-dash]PMes* (1, quin = 2-quinolinyl) and its coordination chemistry with Rh(I) was investigated. In this study, we present the synthesis and characterisation of iridium(I) complex [(quin-CH[double bond, length as m-dash]PMes*)2IrCl] (5), which showed a versatile reactivity upon chloride abstraction with AgOTf in different coordinating solvents affording pyridine-coordinated cationic Ir(I) complex [(quin-CH[double bond, length as m-dash]PMes*)2Ir(py)][OTf] (6) and C–H bond activated cyclometallated Ir(III)-hydrido complex 8. Treatment of complex 5 with CO, (CH3)2Mg or NaN3, respectively, produced three types of five-coordinate Ir(I) complexes 9, 10 and 11 in excellent yields. Complex 6 was found to be less active as a catalyst in the N-alkylation of aniline with benzyl alcohol than complex 5, likely due to the instability of Ir complex 6 in the presence of base at higher temperatures. Complex 5 has also been tested as a catalyst in the Guerbet-type coupling of methanol and ethanol to iso-butanol, which is a promising biofuel candidate, and showed good conversion and selectivity towards the desired iso-butanol.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	Royal Society of Chemistry
ISSN:	2052-1553
Funders:	LIKAT
Date of First Compliant Deposit:	4 May 2023
Date of Acceptance:	21 March 2023
Last Modified:	11 Nov 2024 02:30
URI:	https://orca.cardiff.ac.uk/id/eprint/159205

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