Beyond Takai's Olefination Reagent: Persistent Dehalogenation Emerges in a Chromium(III)‐μ
<sub>3</sub>
‐Methylidyne Complex
作者:Simon Trzmiel、Jan Langmann、Daniel Werner、Cäcilia Maichle‐Mössmer、Wolfgang Scherer、Reiner Anwander
DOI:10.1002/anie.202106608
日期:2021.9
with alkali-metal cyclopentadienides generates isostructural half-sandwich chromium(III)-μ3-methylidynes [CpR3Cr3(μ2-Cl)3(μ3-CH)] (CpR=C5H5, C5Me5, C5H4SiMe3). 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-C5H4SiMe3)CrCl(μ2-Cl)2Li(thf)2]. The Cl/CpR exchange drastically changed the ambient-temperature
CHI 3与六当量的 CrCl 2在 THF 中低温反应得到 [Cr 3 Cl 3 (μ 2 -Cl) 3 (μ 3 -CH)(thf) 6 ] 作为第一个可分离的高产率 Cr III μ 3 -亚甲基络合物。通过盐复分解用碱金属环戊二烯化物取代末端氯配体,生成同构半夹心铬(III)-μ 3 -亚甲基[Cp R 3 Cr 3 (μ 2 -Cl) 3 (μ 3 -CH)] (Cp R =C 5 H 5 、C 5 Me 5 、C 5 H 4 SiMe 3 )。鉴定了 Cl/Cp R交换反应的副产物和分解产物,并对其结构进行了表征 [Cr 4 (μ 2 -Cl) 4 (μ 2 -I) 2 (μ 4 -O)(thf) 4 ] 和 [(η 5 -C 5 H 4 SiMe 3 )CrCl(μ 2 -Cl) 2 Li(thf) 2 ]。 Cl/Cp R交换极大地改变了环境温度有效磁矩μ eff从9.30/9