Investigations into the stability of tethered palladium(II) pincer complexes during heck catalysis

William J. Sommer; Kunquan Yu; John S. Sears; Yaying Ji; Xiaolai Zheng; Robert J. Davis; C. David Sherrill; Christopher W. Jones; Marcus Week

doi:10.1021/om048992v

Investigations into the stability of tethered palladium(II) pincer complexes during heck catalysis

William J. Sommer, Kunquan Yu, John S. Sears, Yaying Ji, Xiaolai Zheng, Robert J. Davis, C. David Sherrill, Christopher W. Jones, Marcus Week

Chemistry

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

Abstract

A variety of palladated PCP pincer complexes are covalently tethered onto polymeric and silica supports via either amide or ether linkages and are evaluated in the Heck reaction of iodobenzene and n-butyl acrylate. The decomposition under reaction conditions of all complexes studied is established through poisoning and kinetic studies. Furthermore, the initial steps of the decomposition pathway of PCP as well as SCS pincer Pd(II) complexes are proposed and validated using in situ NMR, mass spectroscopy, and XAS as well as computational methods. These findings together with our previous reports strongly suggest that all Pd(II) pincer complexes are simply precatalysts during the Heck reaction that decompose to form catalytically active Pd(0) species.

Original language	English (US)
Pages (from-to)	4351-4361
Number of pages	11
Journal	Organometallics
Volume	24
Issue number	18
DOIs	https://doi.org/10.1021/om048992v
State	Published - Aug 29 2005

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om048992v

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abstract = "A variety of palladated PCP pincer complexes are covalently tethered onto polymeric and silica supports via either amide or ether linkages and are evaluated in the Heck reaction of iodobenzene and n-butyl acrylate. The decomposition under reaction conditions of all complexes studied is established through poisoning and kinetic studies. Furthermore, the initial steps of the decomposition pathway of PCP as well as SCS pincer Pd(II) complexes are proposed and validated using in situ NMR, mass spectroscopy, and XAS as well as computational methods. These findings together with our previous reports strongly suggest that all Pd(II) pincer complexes are simply precatalysts during the Heck reaction that decompose to form catalytically active Pd(0) species.",

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AU - Sommer, William J.

AU - Yu, Kunquan

AU - Sears, John S.

AU - Ji, Yaying

AU - Zheng, Xiaolai

AU - Davis, Robert J.

AU - Sherrill, C. David

AU - Jones, Christopher W.

AU - Week, Marcus

PY - 2005/8/29

Y1 - 2005/8/29

N2 - A variety of palladated PCP pincer complexes are covalently tethered onto polymeric and silica supports via either amide or ether linkages and are evaluated in the Heck reaction of iodobenzene and n-butyl acrylate. The decomposition under reaction conditions of all complexes studied is established through poisoning and kinetic studies. Furthermore, the initial steps of the decomposition pathway of PCP as well as SCS pincer Pd(II) complexes are proposed and validated using in situ NMR, mass spectroscopy, and XAS as well as computational methods. These findings together with our previous reports strongly suggest that all Pd(II) pincer complexes are simply precatalysts during the Heck reaction that decompose to form catalytically active Pd(0) species.

AB - A variety of palladated PCP pincer complexes are covalently tethered onto polymeric and silica supports via either amide or ether linkages and are evaluated in the Heck reaction of iodobenzene and n-butyl acrylate. The decomposition under reaction conditions of all complexes studied is established through poisoning and kinetic studies. Furthermore, the initial steps of the decomposition pathway of PCP as well as SCS pincer Pd(II) complexes are proposed and validated using in situ NMR, mass spectroscopy, and XAS as well as computational methods. These findings together with our previous reports strongly suggest that all Pd(II) pincer complexes are simply precatalysts during the Heck reaction that decompose to form catalytically active Pd(0) species.

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Investigations into the stability of tethered palladium(II) pincer complexes during heck catalysis

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