Controlled Mono- and Double-Insertion of Sulfonamide Fragments into Ni–S Bonds of Nickel(II) Dithiocarbamate Complexes via Sulfonyl Azide Reactivity

Controlled Mono- and Double-Insertion of Sulfonamide Fragments into Ni–S Bonds of Nickel(II) Dithiocarbamate Complexes via Sulfonyl Azide Reactivity

Detaylı Bibliyografya
Parent link:Inorganic Chemistry.— .— Washington: ACS Publications
Vol. 64, iss. 23.— 2025.— P. 11867-11879
Diğer Yazarlar: Ignatov E. V. Eugene, Zelenkov L. E. Lev, Baykov S. V. Sergey Valentinovich, Shurikov M. K. Matvey Konstantinovich, Semenov A. V. Artem Valerjevich, Bokach N. A. Nadezhda Arsenjevna, Postnikov P. S. Pavel Sergeevich, Kukushkin V. Yu. Vadim Yurjevich
Özet:Title screen
A novel approach for controlled mono- and double-insertion of sulfonamide fragments into Ni–S bonds of [Ni(S2CNR2)2] complexes has been developed using aryl and alkyl sulfonyl azides as sulfonamide sources. The reaction selectivity is governed by the choice of solvent (hexafluoro-2-propanol for the monoinsertion versus isopropanol for the double-insertion) and temperature (50 and 80 °C, respectively). This method provides convenient access to previously unreported monoinsertion products [NiL(S2CNR2)] along with the double-insertion complexes [NiL2] (L = NSO2(R’)S2NR2) under mild conditions. The scope of the reaction was demonstrated using 18 sulfonyl azides and 6 nickel(II) dithiocarbamates, affording the target complexes (38 examples) isolated in 9–97% yields. The method’s practicality was confirmed through gram-scale syntheses of three representative examples (72, 76, and 92%). X-ray diffraction analysis of 15 new complexes revealed that sulfonamide fragments occupy axial positions relative to the dithiocarbamate plane, with the modified C–S bonds showing inequivalent lengths (1.76–1.78 Å for C–SN vs ∼ 1.71 Å for C–SNi). Mechanistic studies uncovered that insertion products can undergo spontaneous disproportionation in solution
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AM_Agreement
Dil:İngilizce
Baskı/Yayın Bilgisi: 2025
Konular:
труды учёных ТПУ
электронный ресурс
Online Erişim:https://doi.org/10.1021/acs.inorgchem.5c01989
Materyal Türü: Elektronik Kitap Bölümü
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=681325

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