Selective carbonylation of benzene to benzaldehyde using a phosphorus–nitrogen PN3P–rhodium(i) complex

Chunhui Zhou; Jinsong Hu; Yuan Wang; Changguang Yao; Priyanka Chakraborty; Huaifeng Li; Chao Guan; Mei-Hui Huang; Kuo-Wei Huang

doi:10.1039/c8qo00892b

Selective carbonylation of benzene to benzaldehyde using a phosphorus–nitrogen PN3P–rhodium(i) complex

Chunhui Zhou, Jinsong Hu, Yuan Wang, Changguang Yao, Priyanka Chakraborty, Huaifeng Li, Chao Guan, Mei-Hui Huang, Kuo-Wei Huang

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

A PN3P pincer ligand (1) bearing dicyclopentylphosphine substituents reacts with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) to produce the complex (PN3P)RhCl (2). Treatment of a benzene solution of 2 with KN(SiMe3)2 stimulates a dearomatization process, and C–H activation of benzene is achieved through the rearomatization of the central pyridine ring. This deprotonation/reprotonation of the NH arm of 2 gives the phenyl complex (PN3P)Rh(C6H5) (3). The subsequent introduction of CO gas into 3 yields the benzoyl complex (PN3P)RhCO (C6H5) (4), which can release benzaldehyde upon treatment with diluted HCl solution and regenerates 2.

Original language	English (US)
Pages (from-to)	721-724
Number of pages	4
Journal	Organic Chemistry Frontiers
Volume	6
Issue number	6
DOIs	https://doi.org/10.1039/c8qo00892b
State	Published - 2019

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financial support from the King Abdullah University of Science and Technology (KAUST) is acknowledged. This work was dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.

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10.1039/c8qo00892b

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@article{1f176f252df542b7b9490b20c5a97206,

title = "Selective carbonylation of benzene to benzaldehyde using a phosphorus–nitrogen PN3P–rhodium(i) complex",

abstract = "A PN3P pincer ligand (1) bearing dicyclopentylphosphine substituents reacts with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) to produce the complex (PN3P)RhCl (2). Treatment of a benzene solution of 2 with KN(SiMe3)2 stimulates a dearomatization process, and C–H activation of benzene is achieved through the rearomatization of the central pyridine ring. This deprotonation/reprotonation of the NH arm of 2 gives the phenyl complex (PN3P)Rh(C6H5) (3). The subsequent introduction of CO gas into 3 yields the benzoyl complex (PN3P)RhCO (C6H5) (4), which can release benzaldehyde upon treatment with diluted HCl solution and regenerates 2.",

author = "Chunhui Zhou and Jinsong Hu and Yuan Wang and Changguang Yao and Priyanka Chakraborty and Huaifeng Li and Chao Guan and Mei-Hui Huang and Kuo-Wei Huang",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support from the King Abdullah University of Science and Technology (KAUST) is acknowledged. This work was dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.",

year = "2019",

doi = "10.1039/c8qo00892b",

language = "English (US)",

volume = "6",

pages = "721--724",

journal = "Organic Chemistry Frontiers",

issn = "2052-4129",

publisher = "Royal Society of Chemistry",

number = "6",

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TY - JOUR

T1 - Selective carbonylation of benzene to benzaldehyde using a phosphorus–nitrogen PN3P–rhodium(i) complex

AU - Zhou, Chunhui

AU - Hu, Jinsong

AU - Wang, Yuan

AU - Yao, Changguang

AU - Chakraborty, Priyanka

AU - Li, Huaifeng

AU - Guan, Chao

AU - Huang, Mei-Hui

AU - Huang, Kuo-Wei

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support from the King Abdullah University of Science and Technology (KAUST) is acknowledged. This work was dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.

PY - 2019

Y1 - 2019

N2 - A PN3P pincer ligand (1) bearing dicyclopentylphosphine substituents reacts with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) to produce the complex (PN3P)RhCl (2). Treatment of a benzene solution of 2 with KN(SiMe3)2 stimulates a dearomatization process, and C–H activation of benzene is achieved through the rearomatization of the central pyridine ring. This deprotonation/reprotonation of the NH arm of 2 gives the phenyl complex (PN3P)Rh(C6H5) (3). The subsequent introduction of CO gas into 3 yields the benzoyl complex (PN3P)RhCO (C6H5) (4), which can release benzaldehyde upon treatment with diluted HCl solution and regenerates 2.

AB - A PN3P pincer ligand (1) bearing dicyclopentylphosphine substituents reacts with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) to produce the complex (PN3P)RhCl (2). Treatment of a benzene solution of 2 with KN(SiMe3)2 stimulates a dearomatization process, and C–H activation of benzene is achieved through the rearomatization of the central pyridine ring. This deprotonation/reprotonation of the NH arm of 2 gives the phenyl complex (PN3P)Rh(C6H5) (3). The subsequent introduction of CO gas into 3 yields the benzoyl complex (PN3P)RhCO (C6H5) (4), which can release benzaldehyde upon treatment with diluted HCl solution and regenerates 2.

UR - http://hdl.handle.net/10754/653003

UR - https://pubs.rsc.org/en/Content/ArticleLanding/2019/QO/C8QO00892B#!divAbstract

UR - http://www.scopus.com/inward/record.url?scp=85061229425&partnerID=8YFLogxK

U2 - 10.1039/c8qo00892b

DO - 10.1039/c8qo00892b

M3 - Article

SN - 2052-4129

VL - 6

SP - 721

EP - 724

JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

IS - 6

ER -

Selective carbonylation of benzene to benzaldehyde using a phosphorus–nitrogen PN3P–rhodium(i) complex

Abstract

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CCDC 1846987: Experimental Crystal Structure Determination : phenyl-{N,N'-(pyridine-2,6-diyl)bis[P,P-dicyclopentyl(phosphinous amide)]}-rhodium

CCDC 1846989: Experimental Crystal Structure Determination : (benzoyl)-{N,N'-(pyridine-2,6-diyl)bis[P,P-dicyclopentyl(phosphinous amide)]}-rhodium benzene tetrahydrofuran solvate

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Selective carbonylation of benzene to benzaldehyde using a phosphorus–nitrogen PN3P–rhodium(i) complex

Abstract

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Datasets

CCDC 1846987: Experimental Crystal Structure Determination : phenyl-{N,N'-(pyridine-2,6-diyl)bis[P,P-dicyclopentyl(phosphinous amide)]}-rhodium

CCDC 1846989: Experimental Crystal Structure Determination : (benzoyl)-{N,N'-(pyridine-2,6-diyl)bis[P,P-dicyclopentyl(phosphinous amide)]}-rhodium benzene tetrahydrofuran solvate

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