title: Mixed aggregates of 1-methoxyallenyllithium with lithium chloride.
abstract: A combined computational and (13)C NMR study was used to investigate the formation of mixed aggregates of 1-methoxyallenyllithium and lithium chloride in tetrahydrofuran (THF) solution. The observed and calculated chemical shifts, as well as the calculated free energies of mixed aggregate formation (MP2/6-31+G(d)), are consistent with the formation of a mixed dimer as the major species in solution. Free energies of mixed dimer, trimer, and tetramer formation were calculated by using the B3LYP and MP2 methods and the 6-31+G(d) basis set. The two methods generated different predictions of which mixed aggregates will be formed, with B3LYP/6-31+G(d) favoring mixed trimers and tetramers in THF solution, and MP2/6-31+G(d) favoring mixed dimers. Formation of the sterically unhindered mixed dimers is also consistent with the enhanced reactivity of these compounds in the presence of lithium chloride. The spectra are also consistent with some residual 1-methoxyallenyllithium tetramer, as well as small amounts of higher mixed aggregates. Although neither computational method is perfect, for this particular system, the calculated free energies derived using the MP2 method are in better agreement with experimental data than those derived using the B3LYP method.
authors.affiliation: Department of Physical, Environmental, and Computer Science, Medgar Evers College, The City University of New York 1638 Bedford Ave., Brooklyn, NY 11225 (USA) E-mail: lpratt@mec.cuny.edu.
authors.forename: Lawrence M
authors.initials: LM
authors.lastname: Pratt
authors.affiliation: Department of Chemistry, University of Hawaii at Manoa 2545 McCarthy Mall, Honolulu, HI 96813 (USA) The University of Hawaii Cancer Center 701 Ilalo Street, Honolulu, HI 96813 (USA) E-mail: tius@hawaii.edu.
authors.forename: Darryl D
authors.initials: DD
authors.lastname: Dixon
authors.affiliation: Department of Chemistry, University of Hawaii at Manoa 2545 McCarthy Mall, Honolulu, HI 96813 (USA) The University of Hawaii Cancer Center 701 Ilalo Street, Honolulu, HI 96813 (USA) E-mail: tius@hawaii.edu.
authors.forename: Marcus A
authors.initials: MA
authors.lastname: Tius
keywords: NMR; aggregation; computational chemistry; mixed aggregates; organolithium compounds