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Ionic Aggregates of Lithium Organocuprates
Author(s) -
Putau Aliaksei,
Wilken Mona,
Koszinowski Konrad
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300804
Subject(s) - chemistry , electrospray ionization , lithium (medication) , ion , tetrahydrofuran , cuprate , mass spectrometry , ionic bonding , ionization , inorganic chemistry , crystal structure , crystallography , organic chemistry , chromatography , materials science , medicine , optoelectronics , doping , solvent , endocrinology
We have used a combination of electrospray ionization mass spectrometry and electrical conductivity measurements to analyze solutions of the Gilman cuprates LiCuR 2 ⋅LiX, with R=Ph, Bu and X=Cl, Br, I, in tetrahydrofuran and have compared our findings with previous results on cyanocuprates LiCuR 2 ⋅LiCN. Among the various polynuclear organocuprate ions observed, Li 2 Cu 3 Ph 6 − , LiCu 4 Ph 6 − , and Cu 5 Ph 6 − are of particular interest because aggregates of the same composition are known from X‐ray crystal structures. Control experiments have indicated that the polynuclear organocuprate anions detected in solution are indeed identical to those formed in the solid state. As abundant ions of the type Li 2 Cu 3 R 6 − are found in solutions of Gilman cuprates and cyanocuprates alike, their possible involvement in organocuprate reactions should be considered. For comparison, we have also included solutions of LiCu(R)I, LiCuX 2 ⋅LiX, LiCuX 2 , and CuCN⋅2 LiX in the present study.