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Full geometry optimizations have been carried out on the CH<jats:sub>2<\/jats:sub><jats:italic>X<\/jats:italic><jats:sup>\u2212<\/jats:sup> anions and the corresponding neutral parent molecules, CH<jats:sub>3<\/jats:sub><jats:italic>X<\/jats:italic>, at HF\/DZP + and MP2\/DZP + levels. Results for substituents from the second (<jats:italic>X<\/jats:italic> = Li\uf8ffF) and third (<jats:italic>X<\/jats:italic> = Na\uf8ffCl) periods provide comparisons of substituent effects of the main group elements of the first four rows of the periodic table on methyl anions. Frequency calculations characterize the nature of stationary points and show pyramidal CH<jats:sub>2<\/jats:sub><jats:italic>X<\/jats:italic><jats:sup>\u2212<\/jats:sup> anion structures to be the most stable unless \u03c0 acceptor interactions (e.g., with BH<jats:sub>2<\/jats:sub>, AlH<jats:sub>2<\/jats:sub>, GaH<jats:sub>2<\/jats:sub>, and InH<jats:sub>2<\/jats:sub> favor planar geometries. The CH<jats:sub>2<\/jats:sub><jats:italic>X<\/jats:italic><jats:sup>\u2212<\/jats:sup> stabilization energies [at QCISD(T)\/DZP + \/MP2\/DZP + + ZPE level for <jats:italic>X<\/jats:italic> = K\uf8ffI and QCISD(T)\/6\u221231 + G*\/MP2\/6\u221231 + G* + ZPE level] for <jats:italic>X<\/jats:italic> = Li\uf8ffCl) also show strong \u03c0\u2010stabilizing effects for the same substituents. With the exception of CH<jats:sub>3<\/jats:sub> and NH<jats:sub>2<\/jats:sub>, all substituents stabilize methyl anions, although the \u03c3 stabilization by OH and F is small. The SiH<jats:sub>3<\/jats:sub>\uf8ffPH<jats:sub>2<\/jats:sub>\uf8ffSH\uf8ffCl, GeH<jats:sub>3<\/jats:sub>\uf8ffAsH<jats:sub>2<\/jats:sub>\uf8ffSeH\uf8ffBr, and SnH<jats:sub>3<\/jats:sub>\uf8ffSbH<jats:sub>2<\/jats:sub>\uf8ffTeH\uf8ffI sets of substituents give stabilization energies between 19 and 30 kcal\/mol. The stability of methyl anions substituted by the halogens and the chalcogens (<jats:italic>X<\/jats:italic> = OH, SH, SeH, and TeH) increases down a group in accord with the increasing substituent polarizability, while for \u03c0 acceptors (BH<jats:sub>2<\/jats:sub>, AlH<jats:sub>2<\/jats:sub>, GaH<jats:sub>2<\/jats:sub>, and InH<jats:sub>2<\/jats:sub>) the stability decreases down a group in line with their \u03c0\u2010accepting ability. \u00a9 1994 by John Wiley &amp; Sons, Inc.<\/jats:p>","DOI":"10.1002\/jcc.540150605","type":"journal-article","created":{"date-parts":[[2005,1,2]],"date-time":"2005-01-02T01:05:08Z","timestamp":1104627908000},"page":"596-626","source":"Crossref","is-referenced-by-count":40,"title":["Structures and stabilization energies of methyl anions with main group substituents from the first five periods"],"prefix":"10.1002","volume":"15","author":[{"given":"Ahmed M.","family":"El\u2010Nahas","sequence":"first","affiliation":[]},{"given":"Paul Von Ragu\u00e9","family":"Schleyer","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,10,19]]},"reference":[{"key":"e_1_2_1_2_2","volume-title":"Fundamental of Carbanion Chemistry","author":"Cram D. 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