Hydrocarbon-Soluble Bis(trimethylsilylmethyl)calcium and Calcium–Iodine Exchange Reactions at sp²‑Hybrized Carbon Atoms

Hydrocarbon-soluble and highly reactive [(L)_xCa­(CH₂SiMe₃)₂] (L = tetrahydropyran, x = 4 (2a); L = tmeda, x = 2 (2b)) is synthesized by the metathesis reaction of Me₃SiCH₂CaI (1-I) with KCH₂SiMe₃. The durability of 2a in tetrahydropyran solution at 0 °C is sufficiently high for subsequent chemical transformations. The reaction of ICH₂SiMe₃ with calcium in diethyl ether yields unique cage compound [(Et₂O)₂Ca­(I)₂·(Et₂O)₂Ca­(I)­(OEt)·(Et₂O)­Ca­(I)­(CH₂SiMe₃)] (3). We demonstrate that alkylcalcium complexes are valuable reagents for calcium–iodine exchange reactions at C_sp²–I functionalities.