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| - Effective Computational Modeling of Constitutional Isomerismand Aggregation States of Explicit Solvates of LithiatedPhenylacetonitrile
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| - We present the first calculations which accurately account for the position of metalation andaggregation state of lithiated nitriles. Solvation is found to be a key determinant of structure. Fiveknown solvates of lithiated phenylacetonitrile were examined computationally to determine theminimum level of theory required to reproduce the observed X-ray and multinuclear NMRstructures. In all cases Hartree−Fock 3-21G energies of explicit solvates calculated at PM3geometries correctly predict the observed N-lithiated constitutional isomer. Selected densityfunctional theory (B3LYP/6-31+G*//PM3) energy calculations reproduce this trend. We also showthat 3-21G//PM3 calculations which do not include explicit solvent molecules, or which includewater as a model for diethyl ether, may lead to incorrect predictions of the preferred constitutionalisomer. 3-21G//PM3 energies also adequately account for observed aggregation states of the TMEDA,diethyl ether, and THF solvates. Finally, calculations of THF-solvated monomers up to the B3LYP/6-31+G*//B3LYP/6-31+G* level indicate a significant (6.8 kcal/mol) preference for N-lithiation.
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