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Title: Transition states for the carboalumination of alkenes and alkynes

Abstract

Ab initio molecular orbital theory was used to characterize stationary points on the potential energy surface for the carboalumination of alkenes and alkynes. Activation energies and entropies of activation were calculated and found to be in good agreement with experimental values. A {pi}-complex between the alkyl aluminum and the substrate is a stable precursor to the transition structure. The transition structures are four-centered. Substituent effects on the transition structure geometries are small and predictable, suggesting that standard values for geometrical parameters for this and related reactions are reasonable. The anomalous relative reactivities of substrates can be explained by considering the reaction to essentially be a nucleophilic attack, rather than an electrophilic one.

Authors:
; ;  [1]
  1. Bryn Mawr Coll., PA (United States). Dept. of Chemistry|[Lawrence Livermore National Lab., CA (United States)
Publication Date:
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
696630
DOE Contract Number:  
W-7405-ENG-48
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 18; Journal Issue: 19; Other Information: PBD: 13 Sep 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ALUMINIUM COMPOUNDS; ALKENES; ALKYNES; ACTIVATION ENERGY; ENTROPY; MOLECULAR STRUCTURE; MOLECULAR ORBITAL METHOD

Citation Formats

Bundens, J.W., Yudenfreund, J., and Francl, M.M. Transition states for the carboalumination of alkenes and alkynes. United States: N. p., 1999. Web. doi:10.1021/om990350y.
Bundens, J.W., Yudenfreund, J., & Francl, M.M. Transition states for the carboalumination of alkenes and alkynes. United States. doi:10.1021/om990350y.
Bundens, J.W., Yudenfreund, J., and Francl, M.M. Mon . "Transition states for the carboalumination of alkenes and alkynes". United States. doi:10.1021/om990350y.
@article{osti_696630,
title = {Transition states for the carboalumination of alkenes and alkynes},
author = {Bundens, J.W. and Yudenfreund, J. and Francl, M.M.},
abstractNote = {Ab initio molecular orbital theory was used to characterize stationary points on the potential energy surface for the carboalumination of alkenes and alkynes. Activation energies and entropies of activation were calculated and found to be in good agreement with experimental values. A {pi}-complex between the alkyl aluminum and the substrate is a stable precursor to the transition structure. The transition structures are four-centered. Substituent effects on the transition structure geometries are small and predictable, suggesting that standard values for geometrical parameters for this and related reactions are reasonable. The anomalous relative reactivities of substrates can be explained by considering the reaction to essentially be a nucleophilic attack, rather than an electrophilic one.},
doi = {10.1021/om990350y},
journal = {Organometallics},
number = 19,
volume = 18,
place = {United States},
year = {1999},
month = {9}
}