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Solutions of 2-lithio-5-methylthiophene (4) were characterized using DNMR techniques and shown to be a mixture of monomer and dimer in THF–Et2O (3:2). The hypervalent iodine ate complex 5 (Ar2I–Li+), a presumed intermediate in the Li–I exchange with 2-iodo-5-methylthiophene, was observed by 13C and 7Li NMR spectroscopy at low temperatures (–130 °C). At higher temperatures, the ate complex coalesced with 2-lithio-5-methylthiophene. A kinetic scheme was developed, which accounts for the exchange of the monomer 4M, dimer 4D, and 2-iodo-5-methylthiophene (6) with the ate complex 5. The rates of the various exchanges were obtained through a DNMR analysis of the variable temperature 13C and 7Li NMR spectra, and the thermodynamic and activation parameters were calculated. The monomer 4M and the ate complex 5 have similar reactivity as aryl donors in the Li–I exchange reaction, but 4M is at least 1000 times as reactive as the dimer 4D towards the iodide.Key words: halogen–metal exchange, lithium iodinate, iodine ate complex, lithium reagent, aggregate reactivity.

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Polymer adsorption characteristics in complex papermaking systems have been elucidated using tagged reagents and the well-established technique of fluorescence microscopy. Interactions between polymers and components of papermaking slurries have been previously well researched, but the theories put forth are usually based on indirect inferences. Moreover, the use of simple model systems often does not permit correlation with real systems. The present study clearly shows that, under shear conditions and time scales prevalent on a paper machine, polymer partitions to inorganic fillers and fiber fines. In the absence of fillers, the polymer adheres to high surface area regions of the fiber, viz., fibrils that result from mechanical fiber processing operations. The roles of surface area, electrostatic interactions, and other papermaking operations are discussed in detail. We believe this study to be the first extension of fluorescence microscopy for visualizing polymer partitioning in complex systems such as papermaking slurries. On the basis of the data provided here, it should be facile to extend this application for studying polymer behavior in other systems such as sludge dewatering and mineral processing.