Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons

Matthew C. Asplund; Preston T. Snee; Jake S. Yeston; Matthew J. Wilkens; Christine K. Payne; Haw Yang; Kenneth T. Kotz; Heinz Frei; Robert G. Bergman; Charles B. Harris

doi:10.1021/ja020418s

Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons

Matthew C. Asplund, Preston T. Snee, Jake S. Yeston, Matthew J. Wilkens, Christine K. Payne, Haw Yang, Kenneth T. Kotz, Heinz Frei, Robert G. Bergman, Charles B. Harris

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

57 Scopus citations

Abstract

The photochemical C-H activation reactions of η³-Tp*Rh(CO)₂ (Tp* = HB-Pz₃*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)₂ (Cp = C₅H₅) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving σ- and π-solvated intermediates. Results for the analogous CpRh(CO)₂ molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in η³-Tp*Rh(CO)₂ studies.

Original language	English (US)
Pages (from-to)	10605-10612
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	124
Issue number	35
DOIs	https://doi.org/10.1021/ja020418s
State	Published - Sep 4 2002
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{5df9aadf821448c084891161abb9d586,

title = "Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons",

abstract = "The photochemical C-H activation reactions of η3-Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)2 (Cp = C5H5) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving σ- and π-solvated intermediates. Results for the analogous CpRh(CO)2 molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in η3-Tp*Rh(CO)2 studies.",

author = "Asplund, {Matthew C.} and Snee, {Preston T.} and Yeston, {Jake S.} and Wilkens, {Matthew J.} and Payne, {Christine K.} and Haw Yang and Kotz, {Kenneth T.} and Heinz Frei and Bergman, {Robert G.} and Harris, {Charles B.}",

year = "2002",

month = sep,

day = "4",

doi = "10.1021/ja020418s",

language = "English (US)",

volume = "124",

pages = "10605--10612",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "35",

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TY - JOUR

T1 - Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons

AU - Asplund, Matthew C.

AU - Snee, Preston T.

AU - Yeston, Jake S.

AU - Wilkens, Matthew J.

AU - Payne, Christine K.

AU - Yang, Haw

AU - Kotz, Kenneth T.

AU - Frei, Heinz

AU - Bergman, Robert G.

AU - Harris, Charles B.

PY - 2002/9/4

Y1 - 2002/9/4

N2 - The photochemical C-H activation reactions of η3-Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)2 (Cp = C5H5) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving σ- and π-solvated intermediates. Results for the analogous CpRh(CO)2 molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in η3-Tp*Rh(CO)2 studies.

AB - The photochemical C-H activation reactions of η3-Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)2 (Cp = C5H5) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving σ- and π-solvated intermediates. Results for the analogous CpRh(CO)2 molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in η3-Tp*Rh(CO)2 studies.

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U2 - 10.1021/ja020418s

DO - 10.1021/ja020418s

M3 - Article

C2 - 12197763

AN - SCOPUS:0037019696

SN - 0002-7863

VL - 124

SP - 10605

EP - 10612

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 35

ER -

Ultrafast UV pump/IR probe studies of C-H activation in linear, cyclic, and aryl hydrocarbons

Abstract

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