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

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

41 Citations (Scopus)

Abstract

A well-characterised 14-electron rhodium phosphine complex, [Rh((PPr3)-Pr-i)(3)][BAr4F], which contains a beta-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh((PPr3)-Pr-i)(2)((PPr2)-Pr-i(C3H5))][BAr4F]; calculations on a model system show that while C-H activation is equally accessible from the beta-CH agostic species or an alternative gamma-CH agostic isomer, subsequent beta-H-transfer can only be achieved along pathways originating from the beta-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

Keywords

C-H ACTIVATION
RHODIUM COMPLEXES
REACTIVITY
BOND
METAL
MIGRATION
CATALYSTS
LIGANDS
IR(III)

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@article{6f74875371d8489fb178be9c3d2af235,

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

abstract = "A well-characterised 14-electron rhodium phosphine complex, [Rh((PPr3)-Pr-i)(3)][BAr4F], which contains a beta-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh((PPr3)-Pr-i)(2)((PPr2)-Pr-i(C3H5))][BAr4F]; calculations on a model system show that while C-H activation is equally accessible from the beta-CH agostic species or an alternative gamma-CH agostic isomer, subsequent beta-H-transfer can only be achieved along pathways originating from the beta-CH agostic form.",

keywords = "C-H ACTIVATION, RHODIUM COMPLEXES, REACTIVITY, BOND, METAL, MIGRATION, CATALYSTS, LIGANDS, IR(III)",

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((PPr3)-Pr-i)(3)][BAr4F], which contains a beta-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh((PPr3)-Pr-i)(2)((PPr2)-Pr-i(C3H5))][BAr4F]; calculations on a model system show that while C-H activation is equally accessible from the beta-CH agostic species or an alternative gamma-CH agostic isomer, subsequent beta-H-transfer can only be achieved along pathways originating from the beta-CH agostic form.

AB - A well-characterised 14-electron rhodium phosphine complex, [Rh((PPr3)-Pr-i)(3)][BAr4F], which contains a beta-CH agostic interaction, is observed to undergo spontaneous dehydrogenation to afford [Rh((PPr3)-Pr-i)(2)((PPr2)-Pr-i(C3H5))][BAr4F]; calculations on a model system show that while C-H activation is equally accessible from the beta-CH agostic species or an alternative gamma-CH agostic isomer, subsequent beta-H-transfer can only be achieved along pathways originating from the beta-CH agostic form.

KW - C-H ACTIVATION

KW - RHODIUM COMPLEXES

KW - REACTIVITY

KW - BOND

KW - METAL

KW - MIGRATION

KW - CATALYSTS

KW - LIGANDS

KW - IR(III)

U2 - 10.1039/b816739g

DO - 10.1039/b816739g

M3 - Article (Academic Journal)

C2 - 19099083

SP - 244

EP - 246

JO - Chemical Communications

JF - Chemical Communications

SN - 1359-7345

IS - 2

ER -

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

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Keywords

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