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二苯并戊搭烯二锂与Cr(CO) (CH CN) 的反应:阴离子氢二苯并戊搭烯基配合物立方四聚体的意外形成

Reactions of Dilithium Dibenzopentalenides with Cr(CO) (CH CN) : Unexpected Formation of a Cubic Tetramer of an Anionic Hydrodibenzopentalenyl Complex.

作者信息

Kuwabara Takuya, Kurokawa Nobuaki, Saito Masaichi

机构信息

Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama-city, Saitama, 338-8570, Japan.

出版信息

Chempluschem. 2017 Jul;82(7):1039-1042. doi: 10.1002/cplu.201700043. Epub 2017 Mar 27.

DOI:10.1002/cplu.201700043
PMID:31961600
Abstract

To explore the coordination chemistry of dibenzopentalene dianion, reactions of two dilithium dibenzopentalenides having different silyl substituents with Cr(CO) (CH CN) were investigated. The products were unexpected anionic complexes, [Li(Et O)] [Cr(η -9-hydrodibenzopentalenyl)(CO) ] . The proton at the 9-position is derived from Cr(CO) (CH CN) , as evidenced by the use of Cr(CO) (CD CN) . The X-ray diffraction analysis revealed that the chromium is coordinated by an anionic five-membered ring of the pentalene skeleton, and the lithium atom is coordinated by oxygen atoms of the carbonyl groups. The complexes form a dimer or a cage-like tetramer via carbonyl-lithium interactions, depending on the bulk of the silyl groups. The cubic tetramer appears to retain its cage structure in nonpolar solvents such as benzene.

摘要

为了探索二苯并戊搭烯二价阴离子的配位化学,研究了两种具有不同硅基取代基的二苯并戊搭烯二锂与Cr(CO)₃(CH₃CN)₃的反应。产物是意想不到的阴离子配合物,即[Li(Et₂O)]₂[Cr(η⁵-9-氢二苯并戊搭烯基)(CO)₃]。9位的质子来源于Cr(CO)₃(CH₃CN)₃,这一点通过使用Cr(CO)₃(CD₃CN)₃得到了证实。X射线衍射分析表明,铬由戊搭烯骨架的阴离子五元环配位,锂原子由羰基的氧原子配位。根据硅基的大小,这些配合物通过羰基-锂相互作用形成二聚体或笼状四聚体。立方四聚体在苯等非极性溶剂中似乎保留了其笼状结构。

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