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.
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.
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.
Physical Description
7 p.
Notes
Reprinted with permission from the Journal of the American Chemical Society. Copyright 2003 American Chemical Society.
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-C₄F₉)₃. 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.
Publication Title:
Journal of the American Chemical Society
Volume:
125
Issue:
14
Page Start:
4318
Page End:
4324
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.
Cooney, Katharine D.; Cundari, Thomas R., 1964-; Hoffman, Norris W.; Pittard, Karl A.; Temple, M. Danielle & Zhao, Yong.A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites,
article,
March 15, 2003;
[Washington, D.C.].
(https://digital.library.unt.edu/ark:/67531/metadc107782/:
accessed April 25, 2024),
University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu;
crediting UNT College of Arts and Sciences.
