Mechanism of Hydrogenolysis of an Iridium Methyl Bond: Evidence for a Methane Complex Intermediate

PDF Version Also Available for Download.

Description

Article on the mechanism of hydrogenolysis of an iridium methyl bond and evidence for a methane complex intermediate.

Physical Description

4 p.: ill.

Creation Information

Campos, Jesus; Kundu, Sabuj; Pahls, Dale R.; Brookhart, Maurice S.; Carmona, Ernesto & Cundari, Thomas R., 1964- January 11, 2013.

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 330 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 on the mechanism of hydrogenolysis of an iridium methyl bond and evidence for a methane complex intermediate.

Physical Description

4 p.: ill.

Notes

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2013 American Chemical Society.

Abstract: Evidence for key σ-complex intermediates in the hydrogenolysis of the irdium methyl bond of (PONOP)Ir(H)(Me)⁺ (1) [PONOP = 2,6 bis(di-tert-butylphosphinito)pyridine] has been obtained. The initially formed η²-H₂ complex, 2, was directly observed upon treatment of 1 with H₂, and evidence for reversible formation of a σ-methane complex, 5, was obtained through deuterium scrambling from η²-D₂ in 2-d₂ into the methyl group of 2 prior to the methane loss. This sequence of reactions was modeled by density functional theory calculations. The transition state for formation of 5 form 2 showed significant shortening of the Ir H bond for the hydrogen being transferred; no true Ir(V) trihydride intermediate could be located. Barrier to methane loss from 2 were compared to those of 1 and the six-coordinate species (PONOP)Ir(H)(Me)(Co)⁺ and (PONOP)Ir(H)-(Me)(Cl).

Source

  • Journal of the American Chemical Society, 2013, Washington D.C.: American Chemical Society, pp. 1217-1220

Language

Item Type

Identifier

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

Publication Information

  • Publication Title: Journal of the American Chemical Society
  • Volume: 135
  • Issue: 4
  • Page Start: 1217
  • Page End: 1220
  • 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

  • January 11, 2013

Added to The UNT Digital Library

  • Aug. 30, 2013, 3:35 p.m.

Description Last Updated

  • Feb. 10, 2015, 3:05 p.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 3
Total Uses: 330

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

Campos, Jesus; Kundu, Sabuj; Pahls, Dale R.; Brookhart, Maurice S.; Carmona, Ernesto & Cundari, Thomas R., 1964-. Mechanism of Hydrogenolysis of an Iridium Methyl Bond: Evidence for a Methane Complex Intermediate, article, January 11, 2013; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc179686/: accessed August 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.