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通过与氢氧化钠的配体交换反应引发的三羰基(环戊二烯酮)铁配合物的脱金属反应——对具有近平面正方形配位钠的配合物的X射线分析

Demetalation of Tricarbonyl(cyclopentadienone)iron Complexes Initiated by a Ligand Exchange Reaction with NaOH-X-Ray Analysis of a Complex with Nearly Square-Planar Coordinated Sodium.

作者信息

Knölker Hans-Joachim, Baum Elke, Goesmann Helmut, Klauss Rüdiger

机构信息

Institut für Organische Chemie der Universität, Richard-Willstätter-Allee, D-76131 Karlsruhe (Germany), Fax: (+49) 721-698-529.

Institut für Anorganische Chemie der Universität, Engesserstrasse, D-76128 Karlsruhe (Germany).

出版信息

Angew Chem Int Ed Engl. 1999 Jul 12;38(13-14):2064-2066. doi: 10.1002/(SICI)1521-3773(19990712)38:13/14<2064::AID-ANIE2064>3.0.CO;2-W.

Abstract

A sequential exchange of one carbonyl ligand by a hydrido ligand with NaOH, and then by an iodo ligand with iodopentane and finally treatment with acid transforms tricarbonyl(η-cyclopentadienone)iron complexes into dicarbonyl(η-hydroxycyclopentadienyl)iodoiron complexes. These iodo complexes demetalate with high selectivity to the corresponding free ligands on contact with air in daylight. Under basic reaction conditions at the stage of the iodo complex an anionic dicarbonyl(η-cyclopentadienone)iodoiron complex is generated, which is dimeric in the solid state and has an almost square-planar arrangement of the ligands at the sodium counterion.

摘要

通过用氢氧化钠将一个羰基配体依次用氢化物配体取代,然后用碘戊烷将其用碘配体取代,最后用酸处理,可将三羰基(η-环戊二烯酮)铁配合物转化为二羰基(η-羟基环戊二烯基)碘铁配合物。这些碘配合物在日光下与空气接触时会以高选择性脱金属生成相应的游离配体。在碘配合物阶段的碱性反应条件下,会生成一种阴离子二羰基(η-环戊二烯酮)碘铁配合物,它在固态时是二聚体,并且在钠抗衡离子处配体具有几乎平面正方形的排列。

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