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异氰酸酯与双（戊搭烯）钛配合物的波动行为及配体依赖性反应活性

Fluctuating Behavior and Ligand-Dependent Reactivity of Isocyanates with Bis(pentafulvene)titanium Complexes.

作者信息

Eilers Marcel, Bötel Tobias, Schwitalla Kevin, Schmidtmann Marc, Beckhaus Rüdiger

机构信息

Institut für Chemie, Carl von Ossietzky Universität Oldenburg, D-26111 Oldenburg, Federal Republic of Germany.

Institut für Anorganische Chemie, Technische Universität Graz, A-8010 Graz, Republic of Austria.

出版信息

Inorg Chem. 2025 Jul 7;64(26):12990-12999. doi: 10.1021/acs.inorgchem.5c00947. Epub 2025 Jun 19.

DOI:10.1021/acs.inorgchem.5c00947
PMID:40538097
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12239070/
Abstract

Reactions of bis(π-η:σ-η-pentafulvene)titanium complexes with isocyanates result in selective insertions of either one or two equivalents of RN═C═O into the two frustrated Ti-C bonds under mild conditions. Depending on the pentafulvene ligand, K- and K-amidato titanium complexes are obtained and comprehensively characterized by single crystal X-ray diffraction and NMR and IR spectroscopy. In case of single insertion products, the reactivity of the second pentafulvene ligand is investigated with respect to E-H cleavage reactions (alcohols, amines) and insertion reactions of multiple-bond-containing substrates (ketones, nitriles). Transformations of the obtained K- to the respective K-amidato complexes are observed and investigated by DFT studies and variable temperature NMR experiments.

摘要

双（π-η:σ-η-戊搭烯）钛配合物与异氰酸酯反应，在温和条件下会使一当量或两当量的RN═C═O选择性插入到两个受阻的Ti-C键中。根据戊搭烯配体的不同，可得到钾盐和钾酰胺基钛配合物，并通过单晶X射线衍射、核磁共振和红外光谱对其进行全面表征。对于单插入产物，研究了第二个戊搭烯配体相对于E-H裂解反应（醇、胺）和含多重键底物（酮、腈）的插入反应的反应活性。通过密度泛函理论研究和变温核磁共振实验观察并研究了所得钾盐配合物向相应钾酰胺基配合物的转化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/b85e8f839b93/ic5c00947_0014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/d5ce8a6ef20a/ic5c00947_0001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/b85e8f839b93/ic5c00947_0014.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/2830042ae84b/ic5c00947_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/fecd471045f5/ic5c00947_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/84a481e6472d/ic5c00947_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/ffe986a565f0/ic5c00947_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/e6fa7f561ca4/ic5c00947_0013.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c1c5/12239070/b85e8f839b93/ic5c00947_0014.jpg

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本文引用的文献

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2
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Chemistry. 2023 May 22;29(29):e202203846. doi: 10.1002/chem.202203846. Epub 2023 Apr 12.
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Selective Conversion of CO into Isocyanate by Low-Coordinate Iron Complexes.低配位铁配合物将 CO 选择性转化为异氰酸酯。
Angew Chem Int Ed Engl. 2018 May 28;57(22):6507-6511. doi: 10.1002/anie.201802357. Epub 2018 Apr 30.
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