The Role of L-Ligands in Silica-Supported Ti Oxo/Imido Heterometathesis Catalysts

IF 3.7 2区化学 Q2 CHEMISTRY, APPLIED

Applied Organometallic Chemistry Pub Date : 2024-09-26 DOI:10.1002/aoc.7746

Nikolai S. Bushkov, Andrey V. Rumyantsev, Andrey V. Pichugov, Anton A. Zhizhin, Dmitry Yu. Aleshin, Evgenii I. Gutsul, Rina U. Takazova, Dinara Kh. Kitaeva, Fedor M. Dolgushin, Roman A. Novikov, Pavel A. Zhizhko, Dmitry N. Zarubin

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引用次数: 0

Abstract

We report here the preparation and characterization of new well-defined silica-supported Ti imido complexes that present an L-ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=NtBu)(Me₂Pyr)(py)₂ (1s), where py is replaced with stronger electron-donating 4-(N,N-dimethylamino)pyridine (2s) or bidentate 2,2′-bipyridine (3s). The materials were characterized with elemental and mass balance analyses and IR and solid-state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L-ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development.

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L 配体在二氧化硅支撑的钛氧/酰亚胺异构催化剂中的作用

我们在此报告了新的定义明确的二氧化硅支撑 Ti 亚胺配合物的制备和表征，这些配合物在目前最活跃的氧化/亚胺异构化催化剂 (≡SiO)Ti(=NtBu)(Me2Pyr)(py)2 (1s) 的结构中呈现出 L 配体的变化、其中，py 被较强的电子捐赠型 4-(N,N-二甲基氨基)吡啶（2s）或双叉 2,2′-联吡啶（3s）取代。通过元素分析、质量平衡分析、红外光谱和固态核磁共振分析对这些材料进行了表征，结果证实了表面钛物种与末端亚氨基配体的选择性形成。对所获材料的氧化/亚胺异构化催化活性的评估表明，L 配体对催化性能有明显的影响。特别是，用较强的捐赠配体取代吡啶会导致活性显著下降。本文从反应机理和对催化剂进一步开发的影响角度对催化结果进行了讨论。

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

Applied Organometallic Chemistry 化学-无机化学与核化学

CiteScore

7.80

自引率

10.30%

发文量

408

审稿时长

2.2 months

期刊介绍： All new compounds should be satisfactorily identified and proof of their structure given according to generally accepted standards. Structural reports, such as papers exclusively dealing with synthesis and characterization, analytical techniques, or X-ray diffraction studies of metal-organic or organometallic compounds will not be considered. The editors reserve the right to refuse without peer review any manuscript that does not comply with the aims and scope of the journal. Applied Organometallic Chemistry publishes Full Papers, Reviews, Mini Reviews and Communications of scientific research in all areas of organometallic and metal-organic chemistry involving main group metals, transition metals, lanthanides and actinides. All contributions should contain an explicit application of novel compounds, for instance in materials science, nano science, catalysis, chemical vapour deposition, metal-mediated organic synthesis, polymers, bio-organometallics, metallo-therapy, metallo-diagnostics and medicine. Reviews of books covering aspects of the fields of focus are also published.