Construction of Bimetallic and Trimetallic Aggregates with a [Y(COT)2]− Building Block: Solid-State Structures and Solution Behavior

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-09-08 DOI:10.1021/acs.organomet.5c00233

Zheng Zhou, , , Aaron J. Babson, , , Zheng Wei, , and , Marina A. Petrukhina*,

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Abstract

Several new bimetallic and trimetallic complexes containing the [Y(COT)₂]⁻ unit in different coordination environments are synthesized and fully characterized using X-ray crystallography and NMR spectroscopy. These complexes include [K([2.2.2]cryptand)][Y(COT)₂] (1), [K(18-crown-6)(THF)][Y(COT)₂] (2), [Y₂K₂(COT)₄(THF)₄] (3), and [YKCa(COT)₃(THF)₃] (4). In the presence of secondary ligands, bimetallic ionic pairs that comprise a [Y(COT)₂]⁻ sandwich and a solvent-wrapped K⁺ ion are formed in 1 and 2. In contrast, 3 represents a bimetallic tetradecker oligomer with two [Y(COT)₂]⁻ units bridged by a K⁺ ion and a terminal [K(THF)₄]⁺ moiety. Complex 4 is a heterotrimetallic triple-decker with an axial arrangement of three metal centers to form [Y(COT)₂K(COT)Ca(THF)₃]. Structural analysis shows the Y–COT_centroid distances in the [Y(COT)₂]⁻ sandwich are equidistant (1.884(6) Å) in 1 but become asymmetric in 2–4 (1.857(3)–1.952(3) Å), reflecting additional external coordination. The two COT rings are parallel in 1 and become increasingly tilted from 0.8 to 27.5° in 2–4, respectively. Multinuclear NMR spectroscopy measurements reveal the solution behavior of the sandwich and heterometallic multidecker COT-based products. The observed NMR spectroscopic trends corroborate with weak interactions between the [Y(COT)₂]⁻ unit and cationic moieties persisting in solutions of 2–4.

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用[Y(COT)2] -构筑块构建双金属和三金属聚集体：固态结构和溶液行为

合成了几种新的含[Y(COT)2]−单元的双金属和三金属配合物，并利用x射线晶体学和核磁共振光谱对其进行了全面表征。这些复合物包括[K((2.2.2)穴状配体)][Y (COT) 2] (1), (K (18-crown-6)(四氢呋喃)][Y (COT) 2] (2), (Y2K2 (COT) 4(四氢呋喃)4)(3),和[YKCa(床)3(四氢呋喃)3](4)。在二级配体的存在下，在1和2中形成了由[Y(COT)2] -三明治和溶剂包裹的K+离子组成的双金属离子对。相反，3代表双金属四分子低聚物，具有两个[Y(COT)2]−单元，由K+离子和末端[K(THF)4]+部分桥接。配合物4是一种杂三金属三层结构，三个金属中心轴向排列形成[Y(COT)2K(COT)Ca(THF)3]。结构分析表明，[Y(COT)2] -夹层中的Y - COT质心距离在1中是等距的（1.884(6)Å），但在2 - 4中变得不对称(1.857（3)-1.952 (3)Å），反映了额外的外部协调。两个COT环在1中平行，在2-4中分别从0.8°到27.5°逐渐倾斜。多核磁共振波谱测量揭示了夹层和异金属多层科特基产品的溶解行为。观察到的核磁共振光谱趋势证实了[Y(COT)2]−单元与阳离子部分之间的弱相互作用在2 - 4溶液中持续存在。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.