Heterolytic CH activation and catalysis by an O-donor iridium-hydroxo complex

William J. Tenn; Kenneth J.H. Young; Jonas Oxgaard; Robert J. Nielsen; William A. Goddard; Roy A. Periana

doi:10.1021/om060657e

Heterolytic CH activation and catalysis by an O-donor iridium-hydroxo complex

William J. Tenn
, Kenneth J.H. Young
, Jonas Oxgaard
, Robert J. Nielsen
, William A. Goddard
, Roy A. Periana

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

Abstract

A well-defined, O-donor ligated iridium hydroxide complex is reported that is competent for benzene CH activation and long-lived catalytic H/D exchange between benzene and water. An inverse dependence of the H/D exchange rate on added pyridine, a kinetic isotope effect (KIE) of 2.65 ± 0.56 for CH activation with 1,3,5-trideuteriobenzene, a KIE of 1.07 ± 0.24 with C ₆H ₆/C ₆D ₆, and DFT calculations are consistent with the CH activation proceeding via rate-determining benzene coordination followed by fast CH cleavage via a σ-bond-metathesis transition state.

Original language	English
Pages (from-to)	5173-5175
Number of pages	3
Journal	Organometallics
Volume	25
Issue number	21
DOIs	https://doi.org/10.1021/om060657e
Publication status	Published - 9 Oct 2006
Externally published	Yes

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title = "Heterolytic CH activation and catalysis by an O-donor iridium-hydroxo complex",

abstract = "A well-defined, O-donor ligated iridium hydroxide complex is reported that is competent for benzene CH activation and long-lived catalytic H/D exchange between benzene and water. An inverse dependence of the H/D exchange rate on added pyridine, a kinetic isotope effect (KIE) of 2.65 ± 0.56 for CH activation with 1,3,5-trideuteriobenzene, a KIE of 1.07 ± 0.24 with C 6H 6/C 6D 6, and DFT calculations are consistent with the CH activation proceeding via rate-determining benzene coordination followed by fast CH cleavage via a σ-bond-metathesis transition state.",

author = "Tenn, \{William J.\} and Young, \{Kenneth J.H.\} and Jonas Oxgaard and Nielsen, \{Robert J.\} and Goddard, \{William A.\} and Periana, \{Roy A.\}",

year = "2006",

month = oct,

day = "9",

doi = "10.1021/om060657e",

language = "English",

volume = "25",

pages = "5173--5175",

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TY - JOUR

T1 - Heterolytic CH activation and catalysis by an O-donor iridium-hydroxo complex

AU - Tenn, William J.

AU - Young, Kenneth J.H.

AU - Oxgaard, Jonas

AU - Nielsen, Robert J.

AU - Goddard, William A.

AU - Periana, Roy A.

PY - 2006/10/9

Y1 - 2006/10/9

N2 - A well-defined, O-donor ligated iridium hydroxide complex is reported that is competent for benzene CH activation and long-lived catalytic H/D exchange between benzene and water. An inverse dependence of the H/D exchange rate on added pyridine, a kinetic isotope effect (KIE) of 2.65 ± 0.56 for CH activation with 1,3,5-trideuteriobenzene, a KIE of 1.07 ± 0.24 with C 6H 6/C 6D 6, and DFT calculations are consistent with the CH activation proceeding via rate-determining benzene coordination followed by fast CH cleavage via a σ-bond-metathesis transition state.

AB - A well-defined, O-donor ligated iridium hydroxide complex is reported that is competent for benzene CH activation and long-lived catalytic H/D exchange between benzene and water. An inverse dependence of the H/D exchange rate on added pyridine, a kinetic isotope effect (KIE) of 2.65 ± 0.56 for CH activation with 1,3,5-trideuteriobenzene, a KIE of 1.07 ± 0.24 with C 6H 6/C 6D 6, and DFT calculations are consistent with the CH activation proceeding via rate-determining benzene coordination followed by fast CH cleavage via a σ-bond-metathesis transition state.

UR - https://www.scopus.com/pages/publications/33750300012

U2 - 10.1021/om060657e

DO - 10.1021/om060657e

M3 - Article

AN - SCOPUS:33750300012

SN - 0276-7333

VL - 25

SP - 5173

EP - 5175

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Heterolytic CH activation and catalysis by an O-donor iridium-hydroxo complex

Abstract

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