A Priori Assessment of the Stereoelectronic Profile of Phosphines and Phosphites

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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.

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7 p.

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Cooney, Katharine D.; Cundari, Thomas R., 1964-; Hoffman, Norris W.; Pittard, Karl A.; Temple, M. Danielle & Zhao, Yong March 15, 2003.

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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.

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7 p.

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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-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.

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  • Journal of the American Chemical Society, 2003, Washington DC: American Chemical Society, pp. 4318-4324

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 125
  • Issue: 14
  • Page Start: 4318
  • Page End: 4324
  • Peer Reviewed: Yes

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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.**

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  • March 15, 2003

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  • Oct. 9, 2012, 10:02 a.m.

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  • April 1, 2014, 3:22 p.m.

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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.]. (digital.library.unt.edu/ark:/67531/metadc107782/: accessed March 26, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.