AI Article Synopsis
- Simple titanium imido halide complexes, like [BrTi(NBu)py], effectively catalyze the formation of unsymmetrical carbodiimides through nitrene transfer from diazenes or azides to isocyanides.
- The reaction works with both alkyl and aryl isocyanides, but yields can be reduced when using diazenes due to product inhibition with less bulky substrates.
- The reaction mechanism involves electron transfer from the -carbodiimide to a titanium-bound azobenzene, which simplifies the process by avoiding high-energy intermediates and highlights the dual role of substrates and products in catalysis.
Article Abstract
Simple Ti imido halide complexes such as [BrTi(N Bu)py] are competent catalysts for the synthesis of unsymmetrical carbodiimides via Ti-catalyzed nitrene transfer from diazenes or azides to isocyanides. Both alkyl and aryl isocyanides are compatible with the reaction conditions, although product inhibition with sterically unencumbered substrates sometimes limits the yield when diazenes are employed as the oxidant. The reaction mechanism has been investigated both experimentally and computationally, wherein a key feature is that the product release is triggered by electron transfer from an -carbodiimide to a Ti-bound azobenzene. This ligand-to-ligand redox buffering obviates the need for high-energy formally Ti intermediates and provides further evidence that substrate and product "redox noninnocence" can promote unusual Ti redox catalytic transformations.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8188836 | PMC |
| http://dx.doi.org/10.1021/acscatal.9b04107 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!