Controlled Mono- and Double-Insertion of Sulfonamide Fragments into Ni–S Bonds of Nickel(II) Dithiocarbamate Complexes via Sulfonyl Azide Reactivity; Inorganic Chemistry; Vol. 64, iss. 23
| Parent link: | Inorganic Chemistry.— .— Washington: ACS Publications Vol. 64, iss. 23.— 2025.— P. 11867-11879 |
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| Beste egile batzuk: | , , , , , , , |
| Gaia: | 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 Текстовый файл AM_Agreement |
| Hizkuntza: | ingelesa |
| Argitaratua: |
2025
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| Gaiak: | |
| Sarrera elektronikoa: | https://doi.org/10.1021/acs.inorgchem.5c01989 |
| Formatua: | Baliabide elektronikoa Liburu kapitulua |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=681325 |