CaltechAUTHORS
  A Caltech Library Service

C−H Bond Activation by Cationic Platinum(II) Complexes: Ligand Electronic and Steric Effects

Zhong, H. Annita and Labinger, Jay A. and Bercaw, John E. (2002) C−H Bond Activation by Cationic Platinum(II) Complexes: Ligand Electronic and Steric Effects. Journal of the American Chemical Society, 124 (7). pp. 1378-1399. ISSN 0002-7863. doi:10.1021/ja011189x. https://resolver.caltech.edu/CaltechAUTHORS:20170321-104910356

[img] PDF (Summary of arene C−H bond activation kinetic data and derivation of the rate law for Scheme 11) - Supplemental Material
See Usage Policy.

298kB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170321-104910356

Abstract

A series of bis(aryl)diimine-ligated methyl complexes of Pt(II) with various substituted aryl groups has been prepared. The cationic complexes [(ArN CR−CR NAr)PtMe(L)]^+[BF_4]- (Ar = aryl; R = H, CH_3; L = water, trifluoroethanol) react smoothly with benzene at approximately room temperature in trifluoroethanol solvent to yield methane and the corresponding phenyl Pt(II) cations, via Pt(IV)-methyl-phenyl-hydrido intermediates. The reaction products of methyl-substituted benzenes suggest an inherent reactivity preference for aromatic over benzylic C−H bond activation, which can however be overridden by steric effects. For the reaction of benzene with cationic Pt(II) complexes bearing 3,5-disubstituted aryl diimine ligands, the rate-determining step is C−H bond activation, whereas for the more sterically crowded analogues with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. This switch is manifested in distinctly different isotope scrambling and kinetic deuterium isotope effect patterns. The more electron-rich the ligand is, as assayed by the CO stretching frequency of the corresponding carbonyl cationic complex, the faster the rate of C−H bond activation. Although at first sight this trend appears to be at odds with the common description of this class of reaction as electrophilic, the fact that the same trend is observed for the two different series of complexes, which have different rate-determining steps, suggests that this finding does not reflect the actual C−H bond activation process, but rather reflects only the relative ease of benzene displacing a ligand to initiate the reaction; that is, the change in rates is mostly due to a ground-state effect. The stability of the aquo complex ground state in equilibrium with the solvento complex increases as the diimine ligand is made more electron-withdrawing. Several lines of evidence, including the mechanism of degenerate acetonitrile exchange for the methyl-acetonitrile Pt(II) cations in alcohol solvents, suggest that associative substitution pathways operate to get the hydrocarbon substrate into, and out of, the coordination sphere; that is, the mechanism of benzene substitution proceeds by a solvent (TFE)-assisted associative pathway.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja011189xDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja011189xPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja011189xPublisherSupporting Information
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2002 American Chemical Society. Received May 14, 2001. Publication Date (Web): January 15, 2002. Support by the National Science Foundation (Grant No. CHE-9807496), Akzo-Nobel, and BP are gratefully acknowledged. We thank Dr. Joseph Sadighi for preparing the diimine ligand 1a and for devising the synthetic route for the preparation of diimine ligands 3.
Funders:
Funding AgencyGrant Number
NSFCHE-9807496
Akzo-NobelUNSPECIFIED
BPUNSPECIFIED
Issue or Number:7
DOI:10.1021/ja011189x
Record Number:CaltechAUTHORS:20170321-104910356
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170321-104910356
Official Citation:C−H Bond Activation by Cationic Platinum(II) Complexes:  Ligand Electronic and Steric Effects H. Annita Zhong, Jay A. Labinger, and John E. Bercaw Journal of the American Chemical Society 2002 124 (7), 1378-1399 DOI: 10.1021/ja011189x
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75271
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 Mar 2017 18:07
Last Modified:15 Nov 2021 16:32

Repository Staff Only: item control page