A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites

Description:

This article discusses research that has demonstrated the utility of a rigorously calibrated, molecular mechanics/semiempirical quantum mechanical protocol for developing stereoelectronic (Tolman) maps for phosphine ligands.

Creator(s):
Creation Date: March 15, 2003
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Cooney, Katharine D.

Carroll College

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Cundari, Thomas R., 1964-

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Hoffman, Norris W.

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Pittard, Karl A.

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Temple, M. Danielle

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Zhao, Yong

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Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
Date(s):
  • Creation: March 15, 2003
Description:

This article discusses research that has demonstrated the utility of a rigorously calibrated, molecular mechanics/semiempirical quantum mechanical protocol for developing stereoelectronic (Tolman) maps for phosphine ligands.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2003 American Chemical Society.

Note:

Abstract: This research has demonstrated the utility of a rigorously calibrated, molecular mechanics/semiempirical quantum mechanical protocol for developing stereoelectronic (Tolman) maps for phosphine ligands. A computational analysis of alkyl and aryl phosphines in common usage suggests that these ligands are quite similar stereoelectronically. A noticeable gap int he Tolman map for common phosphines is observed for large, electron-poor phosphines. Several candidates meeting these criteria were identified, the most promising of which is P(t-Cā‚„Fā‚‰)ā‚ƒ. Phosphines in which the phosphorus participates in a ring, which comprise a very small subset of reported phosphines, have very interesting stereoelectronic properties, particularly those in which the ligating phosphorus is part of a three-membered ring. In terms of steric properties, the symmetric deformation coordinate proposed by Orpen and co-workers on the basis of crystallographic studies is calculated with sufficient accuracy using PM3(tm) to allow good confidence in predictions of novel phosphines. For quantification of the electronic properties of phosphines, the authors analyzed changes in the CO stretching frequency upon changing the ancillary phosphine ligands.

Physical Description:

7 p.

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Subject(s):
Keyword(s): stereoelectronic profiles | phosphines | phosphites | ligands
Source: Journal of the American Chemical Society, 2003, Washington DC: American Chemical Society, pp. 4318-4324
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja021254i
  • ARK: ark:/67531/metadc107782
Resource Type: Article
Format: Text
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Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 125
Issue: 14
Page Start: 4318
Page End: 4324
Peer Reviewed: Yes