Surajit Das, Jayanta Bag, Sayan Sarkar, Anindita Das, Kuntal Pal
{"title":"配体电子效应对Ni(II)-叠氮酮配合物与炔的iClick反应的影响:合成、结构、表征和动力学研究。","authors":"Surajit Das, Jayanta Bag, Sayan Sarkar, Anindita Das, Kuntal Pal","doi":"10.1002/asia.202500597","DOIUrl":null,"url":null,"abstract":"<p><p>The synthesis and characterization of two new square planer Ni(II)-azido complexes [Ni(N<sub>3</sub>)(L)]<sup>-1</sup> of 1-N<sub>3</sub> and 2-N<sub>3</sub> using electronically varied N/S/O donor tridentate ligands (where H<sub>2</sub>L<sup>OMe</sup>: (E)-2-(((2-mercaptophenyl)imino)methyl)-6-methoxyphenol), H<sub>2</sub>L<sup>t</sup> <sup>Bu</sup>: (E)-2,4-di-tert-butyl-6-(((2-mercaptophenyl)imino)methyl)phenol) were reported. Azido moiety in Ni-azido complexes was found as more dipolar than free azide ion. Six number of [3+2] cycloaddition coupling product of 1-N<sub>3</sub>/2-N<sub>3</sub> and three different alkynes were isolated and well characterized as [Ni(triazolate)(L)]<sup>-1</sup> (1<sup>/</sup> <sup>t</sup> <sup>Bu</sup>-T) complexes. In triazolate complexes originated from terminal alkyne, the triazolate ligand was coordinated via the N1-T atom whose (1-T<sup>2</sup>) crystal structure was presented. The triazolato products of symmetrical and unsymmetrical nonterminal alkynes were isolated as N2-T mode of binding. The conversion of N1-T/N3-T to N2-T as well as the stability in a particular mode of binding was proposed as thermal control of their equilibrium based on the variable temperature <sup>19</sup>F NMR studies on 1-T<sup>3</sup>/2-T<sup>3</sup>. The detail kinetic studies resulted that the reaction with methyl propiolate follows zero-order rate law, whereas other two alkynes showed first-order rate. Mostly, the electron-poor ethyl-4,4,4-trifluorobut-2-ynoate always react faster than dimethyl but-2-ynedioate, and Ni(II)-azido complex with L<sup>t</sup> <sup>Bu</sup> ligated always react with a particular alkyne in a faster rate than the same of L<sup>OMe</sup>.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00597"},"PeriodicalIF":3.5000,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Influence of the Ligand's Electronic Effect on iClick Reaction of Ni(II)-Azido Complexes with Alkynes: Synthesis, Structure, Characterization, and Kinetic Studies.\",\"authors\":\"Surajit Das, Jayanta Bag, Sayan Sarkar, Anindita Das, Kuntal Pal\",\"doi\":\"10.1002/asia.202500597\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The synthesis and characterization of two new square planer Ni(II)-azido complexes [Ni(N<sub>3</sub>)(L)]<sup>-1</sup> of 1-N<sub>3</sub> and 2-N<sub>3</sub> using electronically varied N/S/O donor tridentate ligands (where H<sub>2</sub>L<sup>OMe</sup>: (E)-2-(((2-mercaptophenyl)imino)methyl)-6-methoxyphenol), H<sub>2</sub>L<sup>t</sup> <sup>Bu</sup>: (E)-2,4-di-tert-butyl-6-(((2-mercaptophenyl)imino)methyl)phenol) were reported. Azido moiety in Ni-azido complexes was found as more dipolar than free azide ion. Six number of [3+2] cycloaddition coupling product of 1-N<sub>3</sub>/2-N<sub>3</sub> and three different alkynes were isolated and well characterized as [Ni(triazolate)(L)]<sup>-1</sup> (1<sup>/</sup> <sup>t</sup> <sup>Bu</sup>-T) complexes. In triazolate complexes originated from terminal alkyne, the triazolate ligand was coordinated via the N1-T atom whose (1-T<sup>2</sup>) crystal structure was presented. The triazolato products of symmetrical and unsymmetrical nonterminal alkynes were isolated as N2-T mode of binding. The conversion of N1-T/N3-T to N2-T as well as the stability in a particular mode of binding was proposed as thermal control of their equilibrium based on the variable temperature <sup>19</sup>F NMR studies on 1-T<sup>3</sup>/2-T<sup>3</sup>. The detail kinetic studies resulted that the reaction with methyl propiolate follows zero-order rate law, whereas other two alkynes showed first-order rate. 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Influence of the Ligand's Electronic Effect on iClick Reaction of Ni(II)-Azido Complexes with Alkynes: Synthesis, Structure, Characterization, and Kinetic Studies.
The synthesis and characterization of two new square planer Ni(II)-azido complexes [Ni(N3)(L)]-1 of 1-N3 and 2-N3 using electronically varied N/S/O donor tridentate ligands (where H2LOMe: (E)-2-(((2-mercaptophenyl)imino)methyl)-6-methoxyphenol), H2LtBu: (E)-2,4-di-tert-butyl-6-(((2-mercaptophenyl)imino)methyl)phenol) were reported. Azido moiety in Ni-azido complexes was found as more dipolar than free azide ion. Six number of [3+2] cycloaddition coupling product of 1-N3/2-N3 and three different alkynes were isolated and well characterized as [Ni(triazolate)(L)]-1 (1/tBu-T) complexes. In triazolate complexes originated from terminal alkyne, the triazolate ligand was coordinated via the N1-T atom whose (1-T2) crystal structure was presented. The triazolato products of symmetrical and unsymmetrical nonterminal alkynes were isolated as N2-T mode of binding. The conversion of N1-T/N3-T to N2-T as well as the stability in a particular mode of binding was proposed as thermal control of their equilibrium based on the variable temperature 19F NMR studies on 1-T3/2-T3. The detail kinetic studies resulted that the reaction with methyl propiolate follows zero-order rate law, whereas other two alkynes showed first-order rate. Mostly, the electron-poor ethyl-4,4,4-trifluorobut-2-ynoate always react faster than dimethyl but-2-ynedioate, and Ni(II)-azido complex with LtBu ligated always react with a particular alkyne in a faster rate than the same of LOMe.
期刊介绍:
Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics.
Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews.
A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal.
Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).