Kinetic and thermodynamic preferences in aryl vs benzylic C-H bond activation with cationic Pt(II) complexes

Journal of the American Chemical Society

Volumn 126, Issue 46, 2004, Pages 15034-15035

  Heyduk, Alan F ^a,b   Driver, Tom G ^a   Labinger, Jay A ^a   Bercaw, John E ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,3,5 TRIMETHYLBENZENE; ALKYLBENZENE; BENZENE; BENZENE DERIVATIVE; LEWIS ACID; METHANE; PARA XYLENE; PLATINUM COMPLEX; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; TOLUENE DERIVATIVE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; ISOMERIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; THERMODYNAMICS;

BENZYL COMPOUNDS; CATIONS, DIVALENT; KINETICS; ORGANOPLATINUM COMPOUNDS; THERMODYNAMICS;

EID: 9344236570     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja045078k     Document Type: Article

References (19)

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14. Experimental details, including detailed procedures, spectroscopic data, kinetics analyses and X-ray crystallographic data are provided in Supporting Material.
15. - (which is stable to reaction conditions) and no deuterium incorporation into the platinum methyl cation.
16. 5e The reason for this difference is not clear; (hopefully) plausible explanations for this observation as well as the unusual isotope effect behavior are offered in Supporting Information.
17. eq ≥ 20 can be assigned to the equilibrium constant relating [2] and [3].
18. -1 (Jones, W. D.; Hessell, E. T. J. Am. Chem. Soc. 1993, 115, 554-562).
19. While methyl C-H activation was not directly observed, exposure of 5 to deuterated alcohols caused deuterium exchange into the methyl group of the complex.