Dimethyl- and bis[(trimethylsilyl)methyl]cuprates show aggregates higher than dimers in diethyl ether: molecular diffusion studies by PFG NMR and aggregation-reactivity correlations.

The molecular sizes of higher aggregates of dimethylcuprates (Me(2)CuLi (1), 1.LiI, and 1.LiCN) and bis[(trimethylsilyl)methyl]cuprates ((Me(3)SiCH(2))(2)CuLi (2), 2.LiI, and 2.LiCN) in diethyl ether (Et(2)O) were determined by pulsed field gradient (PFG) NMR diffusion measurements. The obtained diffusion coefficients show molecular sizes larger than those of dimers for all systems. In these higher aggregates, steric hindrance and dilution reduce aggregation, whereas LiCN increases it. The molecular sizes were first determined by a spherical model-free approach and then refined by structure models of higher aggregates. These models were built by a combination of diffusion results, known NMR studies, and crystal structures. Thus, polymeric chains with homodimeric cores connected by solvent (salt-free case) or solvent and salt (salt-containing case) were proposed. These models were confirmed by a solvation analysis, whereby the number of solvent molecules attached to the aggregates was determined by a weighted average study. On the basis of these structure models, the number of repetition units (length index) was determined to be between 1.3 and 5.2, with the general trends in aggregation independent of the structure model used. A combined analysis of the determined length indices and known relative reactivities led for the first time to a correlation between higher aggregation and reactivity of dimethylcuprates in the addition reaction with enones: aggregates higher than dimers reduce the reactivity. Consequently, despite their consistent homodimeric core structures, for the first time the remaining reactivity differences between iodo- and cyanodimethylcuprates in Et(2)O are explained by the difference in their aggregation.