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Addition of 1 equiv of polydentate amine or ether donor solvent to hydrocarbon solutions of lithium hexamethydisilazide (LHMDS) yields a variety of complexes with different aggregation states. X-ray crystallographic analyses have been carried out on six new compounds revealing three-and four-coordinate monomers, η 1 -coordinated mono-and disolvated dimers, and polymers of dimers. PM3 calculations were able to locate minima for a variety of possible structures for the ligands N,N,N′,N′-tetramethylethylenediamine and 1,2-dimethoxyethane. However, the heats of formation from these calculations are found to be unreliable in predicting the relative stabilities of the isomers. Single point ab initio calculations at the 6-31G* level on the PM3 optimized structures give energies which correspond well to the known aggregation states of LHMDS species. Deaggregation from dimers to monomers appears to be driven by a combination of steric, electronic, and chelate effects.

The four Trp dipoles in the gramicidin A (gA) channel modulate channel conductance, and their side chain conformations should therefore be important, but the energies of different conformations are unknown. A conformational search for the right-handed helix based on molecular mechanics in vacuo yielded 46 conformations within 20 kcal/mol of the lowest energy conformation. The two lowest energy conformations correspond to the solid-state and solution-state NMR conformations, suggesting that interactions within the peptide determine the conformation. For representative conformations, the electrostatic potential of the Trp side chains on the channel axis was computed. A novel application of the image-series method of. Biophys. J. 9:1160-1170) was introduced to simulate the polarization of bulk water by the Trp side chains. For the experimentally observed structures, the CHARm toph19 potential energy (PE) of a cation in the channel center is -1.65 kcal/mol without images. With images, the PE is -1.9 kcal/mol, demonstrating that the images further enhance the direct dipole effect. Nonstandard conformations yielded less favorable PEs by 0.4-1.1 kcal/mol.

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Aggregates consisting of lithium halides with either lithium amides or lithium enolates have been characterized by X-ray crystallography. Two structural types, solvated heterodimers and heterotrimers, have been found for halide/amide combinations. Two compounds containing both lithium halide and lithium enolate have also been identified as heterodimers. Using this information, we propose a reaction sequence for enolization and subsequent aldol addition reaction involving halide-containing aggregates. An ab initio and PM3 theoretical study of model systems shows that solvated heterodimers between LiBr and either LiNH2 or LiOC(H)=CH2 are favored over the respective homodimers. Calculations reveal a stable eight-membered ring transition state for the enolization step between LiCl·LiNH2 and acetaldehyde. Two independent transition states, a 4,8 and a 4,4,6 ring system, were calculated for the model reaction between the heterotrimer [(LiNH2)2·LiCl] and acetaldehyde. Dissociation of donor solvent was computed to require more energy for heterodimers than for homodimers.

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