An Investigation of the Structural Diversities of Lithiated HMPA Complexes of o-Mercaptopyridine and Trithiocyanuric Acid: Syntheses, Crystal structures and Model Molecular Orbital Calculations

Reaction of o-mercaptopyridine (o-MPH) and trithiocyanuric acid (TTCyH₃) with one equivalent of BuⁿLi in the presence of HMPA yields the mono-lithiated salts MPLi.HMPA (1) and TTCyH₂Li.2HMPA (2) respectively, which have been characterised by NMR spectroscopy and X-ray crystallography. Reaction of three equivalents of BuⁿLi with anhydrous TTCyH₃ in THF yields the tri-lithiated species TTCyLi₃.4THF (3). In all three compounds the lithium centres have N,S-bridged coordination modes. Whereas 1 is dimeric in the solid state, 2 has an unusual monomeric structure and 3, which is a very rare example of a structurally characterised tri-lithiated compound, has an unprecedented polymeric structure incorporating (NCSLi)_n (n = 1, 2) rings. The structural diversities displayed by 1 and 2 have been probed, and thereby in part rationalised, by ab initio (6-31G*/RHF, 6-31G**/RHF and 6-31G*/MP2 levels) MO calculations on both their thio-keto and thiol isomers and on their uncomplexed and complexed lithiated derivatives. In particular, the optimised structures predict and reproduce the N,S-bridging coordination modes found for lithium and explain why structure 1 is dimeric whereas 2 is monomeric.Electronic Supplementary Material available.