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The B3LYP/6-311++G(d,p) calculations show that when the allyl anion attacks the central N atom of N2.O, the resultant adduct formation is only 4.7 kcal mol-1 exothermic. Thus, this adduct ion is not considered further. Also, see ref 13 and Barlow, S. E, Bierbaum, V. M. J. Chem. Phys. 1990, 92, 3442 for the discussion of the site of N2O reaction with ions
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The B3LYP/6-311++G(d,p) energy optimization has been performed under Cs symmetry for the H2O complex. A low imaginary frequency has been found in the harmonic frequency analysis at the stationary point with respect to hindered rotation around the OH bond. Thus, the potential energy minimum is located at C1 symmetry, but energy lowering from the Cs to C1 geometry is 0.1 kcal mol-1? or less in magnitude. The reported value is that for the Cs symmetry
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We have sought a transition state for N2 elimination from the 1-diazomethylvinyl anion under Cs symmetry. Two imaginary frequencies have been found at the stationary point. One is associated with an in-plane CN stretching mode which must directly represent the N2 dissociation coordinate. The other is an out-of-plane mode which guides the C 3H3 ion fragment into the optimum geometry of the allenyl anion. Thus, the reported value, which is for this Cs, saddle point, should represent an upper bound for the actual transition state
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The reaction enthalpies for the CID processes were derived from the standard enthalpies of formation and the deprotonation enthalpies of the relevant species available in NIST Standard Reference Database Number 69, June 2005 Release.
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