Thermodynamics, Kinetics, and Mechanism of (silox)3M(olefin) to (silox)3M(alkylidene) Rearrangements (silox = tBu3SiO; M = Nb, Ta)

PDF Version Also Available for Download.

Description

Article discussing the thermodynamic, kinetic, and mechanism of (silox)3M(olefin) to (silox)3M(alkylidene) rearrangements (silox = tBu3SiO; M = Nb, Ta).

Physical Description

22 p.

Creation Information

Hirsekorn, Kurt F.; Veige, Adam S.; Marshak, Michael P.; Koldobskaya, Yelena; Wolczanski, Peter T.; Cundari, Thomas R., 1964- et al. March 10, 2005.

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 459 times , with 15 in the last month . 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 the thermodynamic, kinetic, and mechanism of (silox)3M(olefin) to (silox)3M(alkylidene) rearrangements (silox = tBu3SiO; M = Nb, Ta).

Physical Description

22 p.

Notes

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2005 American Chemical Society.

Abstract: Olefin complexes (silox)3M(ole) (silox = tBu3SiO; M = Nb (1-ole), Ta (2-ole); ole = C2H4, C2H3Me, C2H3Et, C2H3C6H4-p-X (X = OMe, H, CF₃), C₂H3tBu, cC5H8, cC6H10, cC7H10 (norbornene)) rearrange to alkylidene isomers (silox)3M(alk) (M = Nb (1=alk), Ta (2=alk); alk = CHMe, CHEt, CHnPr, CHCH2C6H4-p-X (X = OMe, H, CF3 (Ta only)), CHCH2tBu, cC5H8, cC6H10, cC7H10 (norbornylidene)). Kinetics and labeling experiments suggest that the rearrangement proceeds via a ơ-abstraction on a silox CH bond by the β-olefin carbon to give (silox)2RM(κ2-O,C-OSitBu2CMe2CH2) (M = Nb (4-R), Ta (6-R); R = Me, Et, nPr, nBu, CH2-CH2C6H4-p-X (X = OMe, H, CF3 (Ta only)), CH2CH2tBu, cC5H9, cC6H11, cC7H11 (norbornyl)). A subsequent α-abstraction by the cylometalated "arm" of the intermediate on an α-CH bond of R generates the alkylidene 1=alk or 2=alk. Equilibrations of 1-ole with ole' to give 1-ole' and ole, and relevant calculations on 1-ole and 2-ole, permit interpretation of all relative ground and transition state energies for the complexes of either metal.

Source

  • Journal of the American Chemical Society, 2005, Washington DC: American Chemical Society, pp. 4809-4830

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: 127
  • Page Start: 4809
  • Page End: 4830
  • Peer Reviewed: Yes

Collections

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

UNT Scholarly Works

The Scholarly Works Collection is home to materials from the University of North Texas community's research, creative, and scholarly activities and serves as UNT's Open Access Repository. It brings together articles, papers, artwork, music, research data, reports, presentations, and other scholarly and creative products representing the expertise in our university community. 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

  • March 10, 2005

Added to The UNT Digital Library

  • March 2, 2012, 11:47 a.m.

Description Last Updated

  • May 27, 2014, 2:32 p.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 15
Total Uses: 459

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

Hirsekorn, Kurt F.; Veige, Adam S.; Marshak, Michael P.; Koldobskaya, Yelena; Wolczanski, Peter T.; Cundari, Thomas R., 1964- et al. Thermodynamics, Kinetics, and Mechanism of (silox)3M(olefin) to (silox)3M(alkylidene) Rearrangements (silox = tBu3SiO; M = Nb, Ta), article, March 10, 2005; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc77135/: accessed May 23, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.