Lithium Bidentate

S.3.2.3. Lithium Borates with Nonaromatic Ligands. The presence of aromatic ligands in Barthel s salts was believed to be responsible for the high melting points and basicity of the borate anions, which in turn translate into moderate or poor solubilities and ion conductivities as well as low anodic stabilities. To avoid use of these bulky aromatic substituents, Xu and Angell synthesized a series of borate anions that are chelated by various alkyl-based bidentate ligands, which serve as electron-withdrawing moieties by the presence of fluorine or carbonyl functionalities. Table 13 lists the... 

Handa et al. reported the synthesis of a phosphorus equivalent of Barthel s salts in which the hexavalent phosphorus(V) was coordinated by three bidentate ligands. 1.2-benzenediolato-O.C7. Its thermal stability is similar to that of its boron counterparts, and moderate ion conductivity was achieved in nonaqueous media. The authors attributed the less-than-satisfactory ion conduction to the large size of the anions, which increased the viscosity of the resultant electrolyte solutions. The anodic stability limit, as measured by voltammetry on a Ni electrode, was below 3.7 V. A preliminary test of this salt in EC/ THF was conducted in a lithium cell using the low potential cathode. V2O5. and the authors believed that this salt could be a superior electrolyte solute, judging from the utilized cell capacity that was close to the theoretical value. 

Other delocalized anions have been investigated as well, such as complexes of indenyl and fluorenyllithium. These data are also included in Table 8. The sole investigated indenyllithium system was the TMEDA complex. It is known from X-ray crystallography that the lithium cation is located above the five-membered ring and that the TMEDA binds in a bidentate fashion . The x value is somewhat larger than for the corresponding cyclopentadienyllithium complexes (entry 9). 

Significant deviations toward decreased stabilities of Li " complexes from a linear relationship between LCB and GB values also appear for several fluorine-substituted compounds while reasonably good correlation is observed for the S=0 (sulfoxides and sulfones) and P=0 bases. Within the class of oxygen bases the ethers give the worst correlation between basicities. This is because the lithium adducts are much more prone to bidentate chelate ethers as is evident by the enhanced stabilities of Li complexes of methoxy- and fluorine-substituted ethers. Their LCBs are therefore significantly higher than predicted from the linear relationship between LCB and GB values for unsubstituted... 

Ai,Ai -Diphenylbenzamidine undergoes metaUation in toluene, the crystalline precipitate (232) is probably polymeric and contains solvating toluene (average 0.7 mol per Li atom). The lithium imidinate solid produced in the presence of HMPA is dimeric (233) whereas the solids obtained in the presence of bidentate and tridentate ligands (e.g. TMEDA and PMDTA) are monomeric (234 and 235). The products were characterized by H NMR spectra and XRD crystallography, except for 232, for which no crystals suitable for XRD could be prepared . 

The spirocyclic structures of 8b, 9b and 10 consist of two zincacyclopentane (8b and 10) or two zincacyclohexane (9b) rings, having the zinc atom in common. Each of the lithium atoms is bonded to the a-carbon atoms of the two metallacycles, while a tetrahedral coordination geometry at lithium is reached by bidentate N—Ei coordination... 

The major structural types found for lithium amide complexes in the solid state are illustrated in Fig. 34. These comprise ladders of limited extent when the L Li ratio is less than 1 1 (Fig. 34a), dimeric (NLi)2 rings, when this ratio is 1 1 and, usually, when the complexants are monodentate (Fig. 34b), and monomers, both contact-ion pairs (CIPs) and solvent-separated ion pairs (SSIPs) (Fig. 34c). Monomers occur always when there are two or more monodentate complexants per Li. This also is usual with bidentate ligands, and is always found when the ligands have higher denticity. 

Table XIII (189-199) gives details of solid-state lithium amide monomeric complexes (69)—(87). These include just three [(79), (80), and (87)] solvent-separated ion pairs. The remainder are contact-ion pairs, each with an (amido)N—Li bond. Association to dimers or higher oligomers is prevented sterically. The size of the R and/or R group in the RR N- anions can lead to monomers even when Li+ is complexed only by a single bidentate (e.g., TMEDA) or by two monodentate (e.g., THF or Et20) ligands. In such cases [(69), (71), (72), (75)-(78), and (81)—(83) ], the lithium centers are only three coordinate. Electronic factors in the anion [notably, B N multiple bonding in (75)—(78) ] also may reduce the charge density at N, and lower the ability to bridge two...

---