2026-04-27T20:19:37Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/760842025-09-23T10:36:45Zcom_10324_1186com_10324_931com_10324_894col_10324_1404

Snapshots of the stopped polymerization of a hindered isocyanide within the coordination sphere of Ni(II) Álvarez Miguel, Lucía Carmen Rodríguez, Clara del Álvarez González, Celedonio Manuel García Rodríguez, Raúl Miguel San José, Daniel Química inorgánica Inorganic carbon compounds Polymers Producción Científica The use of cationic Ni(II) complexes containing dialkyldithiophosphate ligands in conjunction with sterically hindered isocyanides suppresses polymerization, allowing the formation of well-defined monomeric cationic Ni(II) complexes 3 that result from the coupling of three isocyanides. These complexes have been characterized, including X-ray structure determination, and represent a snapshot of the first steps of the polymerization of isocyanide. Studies via X-ray, IR, and NMR seem to indicate that the key active species in the Ni(II)-catalyzed isocyanide polymerization and its so-called “merry-go-round” mechanism is not a carbene, as has been proposed, but actually a formamidinyl species. The use of the most sterically congested set of ligands enabled the isolation of the intermediate species 4c, which contains only two coupled isocyanides and can be used in the stepwise and controlled synthesis of a rare mixed Ni(II) complex 5 by using two different isocyanides. 2025-06-23T10:51:09Z 2025-06-23T10:51:09Z 2025 info:eu-repo/semantics/article Inorganic Chemistry, 2025, vol. 64, n. 11, p. 5532–5542 0020-1669 https://uvadoc.uva.es/handle/10324/76084 10.1021/acs.inorgchem.4c05461 5532 11 5542 Inorganic Chemistry 64 1520-510X eng https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05461?ref=PDF info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/4.0/ © 2025 American Chemical Society Atribución 4.0 Internacional American Chemical Society SI