{"title":"Examination of Dianionic Diamide Ligand Structural Effects on Ti-Catalyzed Hydrohydrazination of Terminal Alkynes","authors":"Partha Sarathi Karmakar, and , Ian A. Tonks*, ","doi":"10.1021/acs.organomet.5c00234","DOIUrl":null,"url":null,"abstract":"<p >Ti-catalyzed alkyne hydrohydrazination of terminal alkynes using 1,1-disubstituted hydrazines is reported. Here, a variety of bi- or tridentate dianionic diamide or diamidoamine ligated Ti═NNPh<sub>2</sub> catalysts were examined, wherein fast and selective Ti═NNPh<sub>2</sub> catalysts have ligands with a “goldilocks” intermediate level of the steric environment. Ti═NNPh<sub>2</sub> catalysts with ligands of high/medium steric bulk showed slower reactivity compared to that of the optimal catalysts. Catalysis with Ti complexes with sterically less encumbered ligands is extremely slow (requiring 5–14 days to completion). Development of a fast and selective diamidoamine catalyst with flanking N-SiMe<sub>2</sub>Ph groups led to an expansion of the hydrazine scope and a structurally diverse set of hydrazones.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 16","pages":"1854–1859"},"PeriodicalIF":2.9000,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00234","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Ti-catalyzed alkyne hydrohydrazination of terminal alkynes using 1,1-disubstituted hydrazines is reported. Here, a variety of bi- or tridentate dianionic diamide or diamidoamine ligated Ti═NNPh2 catalysts were examined, wherein fast and selective Ti═NNPh2 catalysts have ligands with a “goldilocks” intermediate level of the steric environment. Ti═NNPh2 catalysts with ligands of high/medium steric bulk showed slower reactivity compared to that of the optimal catalysts. Catalysis with Ti complexes with sterically less encumbered ligands is extremely slow (requiring 5–14 days to completion). Development of a fast and selective diamidoamine catalyst with flanking N-SiMe2Ph groups led to an expansion of the hydrazine scope and a structurally diverse set of hydrazones.
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.
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