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

ABSTRACT: 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.

SUBMITTER: Trzmiel S 

PROVIDER: S-EPMC8456800 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Beyond Takai's Olefination Reagent: Persistent Dehalogenation Emerges in a Chromium(III)-μ<sub>3</sub> -Methylidyne Complex.

Trzmiel Simon S   Langmann Jan J   Werner Daniel D   Maichle-Mössmer Cäcilia C   Scherer Wolfgang W   Anwander Reiner R  

Angewandte Chemie (International ed. in English) 20210801 36

Reaction of CHI<sub>3</sub> with six equivalents of CrCl<sub>2</sub> in THF at low temperatures affords [Cr<sub>3</sub> Cl<sub>3</sub> (μ<sub>2</sub> -Cl)<sub>3</sub> (μ<sub>3</sub> -CH)(thf)<sub>6</sub> ] as the first isolable high-yield Cr<sup>III</sup> μ<sub>3</sub> -methylidyne complex. Substitution of the terminal chlorido ligands via salt metathesis with alkali-metal cyclopentadienides generates isostructural half-sandwich chromium(III)-μ<sub>3</sub> -methylidynes [Cp<sup>R</sup> <sub>3</s  ...[more]

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