Beyond Takai's Olefination Reagent: Persistent Dehalogenation Emerges in a Chromium(III)-μ3 -Methylidyne Complex.

Reaction of CHI3 with six equivalents of CrCl2 in THF at low temperatures affords [Cr3 Cl3 (μ2 -Cl)3 (μ3 -CH)(thf)6 ] as the first isolable high-yield CrIII μ3 -methylidyne complex. Substitution of the terminal chlorido ligands via salt metathesis with alkali-metal cyclopentadienides generates isostructural half-sandwich chromium(III)-μ3 -methylidynes [CpR 3 Cr3 (μ2 -Cl)3 (μ3 -CH)] (CpR =C5 H5 , C5 Me5 , C5 H4 SiMe3 ). Side and decomposition products of the Cl/CpR exchange reactions were identified and structurally characterized for [Cr4 (μ2 -Cl)4 (μ2 -I)2 (μ4 -O)(thf)4 ] and [(η5 -C5 H4 SiMe3 )CrCl(μ2 -Cl)2 Li(thf)2 ]. The Cl/CpR exchange drastically changed the ambient-temperature effective magnetic moment μeff from 9.30/9.11 μB (solution/solid) to 3.63/4.32 μB (CpR =C5 Me5 ). Reactions of [Cr3 Cl3 (μ2 -Cl)3 (μ3 -CH)(thf)6 ] with aldehydes and ketones produce intricate mixtures of species through oxy/methylidyne exchange, which were partially identified as radical recombination products through GC/MS analysis and 1 H NMR spectroscopy.