Molecular and Electronic Structure of Linear Uranium Metallocenes Stabilized by Pentabenzyl-Cyclopentadienyl Ligands

Löffler S, Heinemann FW, Carpentier A, Maron L, Meyer K (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Organometallics American Chemical Society

Abstract

We report a series of uranium complexes stabilized by the pentakis-benzyl-derivatized cyclopentadienyl ligand, Cp-Bn5. Treatment of [UCl4] and [UI3(1,4-dioxane)(1,5)] with 2 equiv of the potassium salt, (CpK)-K-Bn5, yielded the corresponding complexes [(CpBn5)(2)UIV(Cl)(2)] (1) and [(CpBn5)2U(III)(I)] (4). Subsequently, tetravalent 1 is either methylated to give [(Cp-Bn5)(2)U-IV(Me)(2)] (2) or reduced to form trivalent [(CpBn5)(2)U-III(mu-Cl)(2)K(OEt2)(3)] (3). Oxidation of 4 with AgI yields [(CpBn5)(2)U-IV(I)(2)] (5), which was found to generate rarely observed, linear uranium metallocenes [(CpBn5)2U(IV)(NCMe)(5)][X](2) (X = PF6- (6), BPh4- (7)) upon abstraction of the iodide ligands with thallium salts in acetonitrile. All complexes were characterized by H-1 NMR spectroscopy, CHN elemental analysis, UV-vis-NIR spectroscopy, and SQUID magnetization measurements. The solid-state molecular structures of 1-7 were determined by single-crystal X-ray diffraction analysis. An in-depth computational analysis revealed the peculiar electronic structure of the linearly coordinated title complex 7 and its closely related, parent [(Cp*)(2)U-IV(NCMe3)(5)](2+) dication.

Authors with CRIS profile

Sascha Löffler Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Université Toulouse III - Paul Sabatier

France (FR)

How to cite

APA:

Löffler, S., Heinemann, F.W., Carpentier, A., Maron, L., & Meyer, K. (2022). Molecular and Electronic Structure of Linear Uranium Metallocenes Stabilized by Pentabenzyl-Cyclopentadienyl Ligands. Organometallics. https://doi.org/10.1021/acs.organomet.2c00217

MLA:

Löffler, Sascha, et al. "Molecular and Electronic Structure of Linear Uranium Metallocenes Stabilized by Pentabenzyl-Cyclopentadienyl Ligands." Organometallics (2022).

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