Synthesis and Characterization of the Organoiodocuprate Complexes [Li(THF)4][2,6-Mes2H3C6Cu2I2] (Mes = C6H2-2,4,6-Me3) and (Et2O)2Li{ICuC6H3-2,6-Trip2} (Trip = C6H2-2,4,6-i-Pr3)

Treatment of CuI with 2 equiv of LiC 6 H 3 -2,6-Mes 2 (Mes = C 6 H 2 -2,4,6-Me 3 ) in Et 2 O/THF solution affords the species [Li(THF) 4 ][2,6-Mes 2 H 3 C 6 Cu 2 I 2 ] ( 1 ), which was characterized by 1 H, 7 Li, and 13 C NMR spectroscopy and by X-ray crystallography. An analogous reaction involving CuI and 1 equiv of LiC 6 H 3 -2,6-Trip 2 (Trip = C 6 H 2 -2,4,6- i -Pr 3 ) gives the contact ion-pair species (Et 2 O)Li{ICuC 6 H 3 -2,6-Trip 2 } ( 2 ), which was characterized similarly. Compounds 1 and 2 represent very rare instances of well-characterized organohalocuprate species. The unique structure of the anion in 1 features two copper iodides bound to the ipso-carbon of the m -terphenyl ligand −C 6 H 3 -2,6-Mes 2 . The organic group interacts almost equally strongly with each copper, and there is a very short Cu−Cu distance of 2.391(3) Å. The copper in compound 2 is bound in an almost linear fashion by an iodide and an ipso-carbon atom from the ligand −C 6 H 3 -2,6-Trip 2 . The iodide is also bound to a lithium ion (which is solvated by two ethers) such that there is an unusually narrow interligand angle Li−I−Cu = 95.5(2)° at the iodide.