THE CARBON-LITHIUM ELECTRON-PAIR BOND IN (CH3LI)(N) (N=1, 2, 4)

The monomer, dimer, and tetramer of methyllithium, (CH3Li)(n) (n = 1, 2, 4), have been studied with use of density-functional (DFT) and conv entional ab initio theory. The energy gain Delta E associated with the formation of (CH3-Li)(n) from n Li-. and n CH3(.) radicals is -45.5, -132.7, and -308.6 kcal/mol for n = 1, 2, and 4 using nonlocal density -functionals and a large, doubly polarized triple-zeta STO basis (NL-S CF/TZ2P). The corresponding dimerization and tetramerization. energies for methyllithium are -41.7 and -126.6 kcal/mol, respectively. The 29 8 K heat of formation of CH3Li(g) is calculated to be 29.2 kcal/mol, u sing experimental Delta H-f values for CH3.(g) and Li-.(g). The low-en ergy lithium 2p orbitals are shown to play an active role in the bondi ng of the methyllithium aggregates and can be viewed as valence orbita ls. A detailed analysis of the carbon-lithium bonding mechanism highli ghts the significant role of covalent contributions. In CH3Li, we find a strongly polar C-Li electron pair bond in which charge is donated f rom Li 2s to the CH3 2a(1)-SOMO. The covalent character is indicated b y 2s +/- 2a(1) mixing and a sizable lithium 2p(z) participation. In (C H3-Li)(4) the carbon-lithium bond is provided by two distinct orbital interactions: (1) an essentially covalent electron pair bond between t he strongly sp hybridized Li-Li and C-C bonding fragment orbitals of t he lithium cluster and the methyl cage, respectively, in Al symmetry; (2) a strongly polar electron pair bond between the corresponding trip ly degenerate Li-Li and C-C antibonding fragment orbital sets in T-2 s ymmetry. The situation is similar for(CH3Li)(2). The electron density is analyzed using atomic charges from the following: (1) the natural p opulation analysis (NPA); (2) the Hirshfeld method; (3) the Mulliken m ethod as well as a modification which we term Modified Mulliken; (4) a scheme which we designate Voronoi deformation density (VDD); the VDD charges monitor the shift of electron density out of (Q > 0) or into ( Q < 0) the Voronoi cell of an atom upon formation of the molecule from the isolated atoms. The degree of ionicity of the carbon-lithium bond decreases from ca. ''50'' down to ''30%'' along CH3Li, (CH3Li)(2), an d (CH3Li)(4), according to the Hirshfeld charges. This agrees with a s imilar trend emerging from the VDD charges as well as with the results of the electronic structure analysis. The NPA charges suggest that th e carbon-lithium bond is ca. ''90%'' ionic and that the degree of ioni city is independent of the size of the aggregate.