Variable temperature H-1- and C-13-NMR spectroscopic analysis of THF and THF-HMPA solutions of stannylcyanocuprates, as well as their addition products to l-alkynyl ethers have been conducted. When prepared in the presence of HMPA, the reagents and addition products formed exist as mixtures in which some free lithium cyanide is present and the remaining cyanide is otherwise complexed. When stannylcyanocuprates were prepared in THF solutions no LiCN was detected. Heteronuclear NMR of the intermediates formed in the low-temperature reaction of a C-13-labeled acetylenic ether with a THF-HMPA solution of stannylcyanocuprate (Bu3Sn)(2)Ch((CN)-C-13)-Li-2 reveals a (CN)-C-13-C-13-vinyl carbon coupling consistent with a vinylcuprate intermediate containing cyanide and a vinyl group bound to a common center. Coupling between a metal bound Sn-119 and C-13-vinyl carbon was observed in the intermediate suggesting these two atoms are bound to a common center. The lack of Sn-119-(CN)-C-13 coupling in the intermediate suggested Sn-119 and (CN)-C-13 were bound to different atoms. Requirements are met in both higher order and lower order cuprate structures. When "Me2Cu((CN)-C-13)Li-2" is prepared in THF, no free LiCN is observed and neither is it generated on addition of HMPA. When Me2Cu((CN)-C-13)Li-2 is prepared in HMPA-containing solutions it exists with the corresponding cyanide-free species and LiCN.