Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate

Adrian B. Chaplin; Amalia I. Poblador-Bahamonde; Hazel A. Sparkes; Judith A.K. Howard; Stuart A. Macgregor; Andrew S. Weller

doi:10.1039/b816739g

Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate

Adrian B. Chaplin
, Amalia I. Poblador-Bahamonde
, Hazel A. Sparkes
, Judith A.K. Howard
, Stuart A. Macgregor
, Andrew S. Weller

School of Chemistry

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

Abstract

A well-characterised 14-electron rhodium phosphine complex, [Rh(P ⁱPr₃)₃][BAr^F₄], which contains a β-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh(PⁱPr₃)₂(P ⁱPr₂(C₃H₅))][BAr^F ₄]; calculations on a model system show that while C-H activation is equally accessible from the β-CH agostic species or an alternative γ-CH agostic isomer, subsequent β-H-transfer can only be achieved along pathways originating from the β-CH agostic form.

Original language	English
Pages (from-to)	244-246
Number of pages	3
Journal	Chemical Communications
Issue number	2
DOIs	https://doi.org/10.1039/b816739g
Publication status	Published - 2009

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@article{e83b8db343b84c36bc9ec389de7c34fd,

title = "Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate",

abstract = "A well-characterised 14-electron rhodium phosphine complex, [Rh(P iPr3)3][BArF4], which contains a β-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh(PiPr3)2(P iPr2(C3H5))][BArF 4]; calculations on a model system show that while C-H activation is equally accessible from the β-CH agostic species or an alternative γ-CH agostic isomer, subsequent β-H-transfer can only be achieved along pathways originating from the β-CH agostic form.",

author = "Chaplin, \{Adrian B.\} and Poblador-Bahamonde, \{Amalia I.\} and Sparkes, \{Hazel A.\} and Howard, \{Judith A.K.\} and Macgregor, \{Stuart A.\} and Weller, \{Andrew S.\}",

year = "2009",

doi = "10.1039/b816739g",

language = "English",

pages = "244--246",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

number = "2",

}

TY - JOUR

T1 - Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate

AU - Chaplin, Adrian B.

AU - Poblador-Bahamonde, Amalia I.

AU - Sparkes, Hazel A.

AU - Howard, Judith A.K.

AU - Macgregor, Stuart A.

AU - Weller, Andrew S.

PY - 2009

Y1 - 2009

N2 - A well-characterised 14-electron rhodium phosphine complex, [Rh(P iPr3)3][BArF4], which contains a β-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh(PiPr3)2(P iPr2(C3H5))][BArF 4]; calculations on a model system show that while C-H activation is equally accessible from the β-CH agostic species or an alternative γ-CH agostic isomer, subsequent β-H-transfer can only be achieved along pathways originating from the β-CH agostic form.

AB - A well-characterised 14-electron rhodium phosphine complex, [Rh(P iPr3)3][BArF4], which contains a β-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh(PiPr3)2(P iPr2(C3H5))][BArF 4]; calculations on a model system show that while C-H activation is equally accessible from the β-CH agostic species or an alternative γ-CH agostic isomer, subsequent β-H-transfer can only be achieved along pathways originating from the β-CH agostic form.

UR - https://www.scopus.com/pages/publications/58049194194

U2 - 10.1039/b816739g

DO - 10.1039/b816739g

M3 - Article

AN - SCOPUS:58049194194

SN - 1359-7345

SP - 244

EP - 246

JO - Chemical Communications

JF - Chemical Communications

IS - 2

ER -

Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate

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