A novel Zirconocene derived from substituted as-indacene: Synthesis, characterization, and DFT insights into its electronic structure and stability

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-06-09 DOI:10.1016/j.ica.2025.122801

Yuvaraja Dibdalli , Cesar Morales-Verdejo , Daniela E. Ortega , Andy Mella , Elies Molins , Sateesha M. Kannakatte , Mahesha , Mungalimane K. Amshumali

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Abstract

We focus on the synthesis, characterization, and theoretical analysis of a novel zirconocene complex derived from substituted 2,7-diethyl-1,8-dihydro-as-indacene (as-Ic'H₂).This complex [(Cp*ZrCl₂)₂-as-Ic´], was synthesized from the dilithiated salt of as-indacene [as-Ic´][Li]₂ with two equivalents of [(Cp*ZrCl₃)]. Comprehensive characterization was performed using ¹H and ¹³C NMR spectroscopy, elemental analysis, and X-ray diffraction. Density Functional Theory (DFT) calculations revealed that the dicationic pathway for ethylene polymerization exhibits enhanced thermodynamic stability and favorable orbital interactions, offering a more efficient initiation process than the cationic pathway. However, higher activation barriers were identified in the dicationic pathway, suggesting that targeted steric modifications could further optimize catalytic performance. These findings provide strategic insights for designing more effective bimetallic zirconocene catalysts.

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一种由取代茚二烯衍生的新锆新世：合成、表征及其电子结构和稳定性的DFT分析

本文研究了一种由取代的2,7-二乙基-1,8-二氢-茚二烯（as-Ic'H2）衍生的新型锆新世配合物的合成、表征和理论分析。该配合物[(Cp*ZrCl2)2-as-Ic´]是由as-茚二烯[as-Ic´][Li]2的稀化盐与两个等价物[(Cp*ZrCl3)]合成的。通过1H和13C NMR谱、元素分析和x射线衍射进行了全面的表征。密度泛函理论（DFT）计算表明，乙烯聚合的双离子途径表现出更强的热力学稳定性和有利的轨道相互作用，提供了比阳离子途径更有效的引发过程。然而，在定向途径中发现了更高的激活障碍，这表明靶向立体修饰可以进一步优化催化性能。这些发现为设计更有效的双金属锆茂催化剂提供了战略见解。

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

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.