C H Bond Activation of Methane by Ptᴵᴵ N-Heterocyclic Carbene Complexes: The Importance of Having the Ligands in the Right Place at the Right Time

PDF Version Also Available for Download.

Description

Article discussing C H bond activation of methane by Ptᴵᴵ N-Heterocyclic carbene complexes.

Physical Description

7 p.: ill.

Creation Information

Prince, Bruce M. & Cundari, Thomas R., 1964- Creation Date: Unknown.

Context

This article is part of the collection entitled: UNT Scholarly Works and was provided by UNT College of Arts and Sciences to Digital Library, a digital repository hosted by the UNT Libraries. It has been viewed 249 times . More information about this article can be viewed below.

Who

People and organizations associated with either the creation of this article or its content.

Authors

Publisher

Provided By

UNT College of Arts and Sciences

The UNT College of Arts and Sciences educates students in traditional liberal arts, performing arts, sciences, professional, and technical academic programs. In addition to its departments, the college includes academic centers, institutes, programs, and offices providing diverse courses of study.

Contact Us

What

Descriptive information to help identify this article. Follow the links below to find similar items on the Digital Library.

Degree Information

Description

Article discussing C H bond activation of methane by Ptᴵᴵ N-Heterocyclic carbene complexes.

Physical Description

7 p.: ill.

Notes

Reprinted with permission from Organometallics. Copyright 2012 American Chemical Society.

Abstract: A DFT study of methane C H activation barriers for neutral NHC Ptᴵᴵ methoxy complexes yielded 22.8 and 26.1 kcal/mol for oxidative addition (OA) and oxidative hydrogen migration (OHM), respectively. Interestingly, this is unlike the case for cationic NHC Ptᴵᴵ methoxy complexes, whereby OHM entails a calculated barrier of 26.9 kcal/mol but the OA barrier is only 14.4 kcal/mol. Comparing transition state (TS) and ground state (GS) geometries implies an 10 kcal/mol "penalty" to the barriers arising from positioning the NHC and OMe ligands into a relative orientation that is preferred in the GS to the orientation that is favored in the TS. The results thus imply an intrinsic barrier arising from C H scission of 15 2 kcal/mol for NHC Ptᴵᴵ methoxy complexes. Calculations show the importance of designing C H activation catalysts where the GS active species is already structurally "prepared" and which either does not need to undergo any geometric perturbations to access the methane C H activation TS or is not energetically prohibited from such perturbations.

Source

  • Organometallics, 2012, Washington DC: American Chemical Society, pp. 1042-1048

Language

Item Type

Identifier

Unique identifying numbers for this article in the Digital Library or other systems.

Publication Information

  • Publication Title: Organometallics
  • Volume: 31
  • Issue: 3
  • Page Start: 1042
  • Page End: 1048
  • Peer Reviewed: Yes

Collections

This article is part of the following collection of related materials.

UNT Scholarly Works

Materials from the UNT community's research, creative, and scholarly activities and UNT's Open Access Repository. Access to some items in this collection may be restricted.

What responsibilities do I have when using this article?

When

Dates and time periods associated with this article.

Creation Date

  • Unknown

Accepted Date

  • January 25, 2012

Added to The UNT Digital Library

  • Sept. 13, 2013, 2:58 p.m.

Description Last Updated

  • March 27, 2014, 3:25 p.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 249

Interact With This Article

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Prince, Bruce M. & Cundari, Thomas R., 1964-. C H Bond Activation of Methane by Ptᴵᴵ N-Heterocyclic Carbene Complexes: The Importance of Having the Ligands in the Right Place at the Right Time, article, Date Unknown; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc181679/: accessed August 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.