Autor segons l'article: Carbo, J; Gomez, M; Hernandez-Prieto, C; Hernan-Gomez, A; Martin, A; Mena, M; Puiggali-Jou, J; Ricart, JM; Santamaria, C
Departament: Química Física i Inorgànica
Autor/s de la URV: Carbó Martin, Jorge Juan / Ricart Pla, Jose Manuel
Paraules clau: Molecular-orbital methods transition-metals side-on reactivity n-2 unit hydride dinitrogen ligand bond-cleavage augmented basis-sets activation
Resum: Hydrogenolysis of a series of alkyl sulfido-bridged tantalum(IV) dinuclear complexes [Ta(η5-C5Me5)R(μ-S)]2 [R = Me, nBu (1), Et, CH2SiMe3, C3H5, Ph, CH2Ph (2), p-MeC6H4CH2 (3)] has led quantitatively to the Ta(III) tetrametallic sulfide cluster [Ta(η5-C5Me5)(μ3-S)]4 (4) along with the corresponding alkane. Mechanistic information for the formation of the unique low-valent tetrametallic compound 4 was gathered by hydrogenation of the phenyl-substituted precursor [Ta(η5-C5Me5)Ph(μ-S)]2, which proceeds through a stepwise hydrogenation process, disclosing the formation of the intermediate tetranuclear hydride sulfide [Ta2(η5-C5Me5)2(H)Ph(μ-S)(μ3-S)]2 (5). Extending our studies toward tantalum alkyl precursors containing functional groups susceptible to hydrogenation, such as the allyl-and benzyl-substituted compounds [Ta(η5-C5Me5)(η3-C3H5)(μ-S)]2 and [Ta(η5-C5Me5)(CH2Ph)(μ-S)]2 (2), enables alternative reaction pathways en route to the formation of 4. In the former case, the dimetallic system undergoes selective hydrogenation of the unsaturated allyl moiety, forming the asymmetric complex [{Ta(η5-C5Me5)(η3-C3H5)}(μ-S)2{Ta(η5-C5Me5)(C3H7)}] (6) with only one propyl fragment. Species 2, in addition to the hydrogenation of one benzyl fragment and concomitant toluene release, also undergoes partial hydrogenation and dearomatization of the phenyl ring on the vicinal benzyl unity to give a η5-cyclohexadienyl complex [Ta2(η5-C5Me5)2(μ-CH2C6H6)(μ-S)2] (7). The mechanistic implications of the latter hydrogenation process are discussed by means of DFT calculations.
Àrees temàtiques: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: j.carbo@urv.cat josep.ricart@urv.cat
Identificador de l'autor: 0000-0002-3945-6721 0000-0002-2610-5535
Data d'alta del registre: 2024-08-03
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c00043
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Inorganic Chemistry. 62 (26): 10100-10109
Referència de l'ítem segons les normes APA: Carbo, J; Gomez, M; Hernandez-Prieto, C; Hernan-Gomez, A; Martin, A; Mena, M; Puiggali-Jou, J; Ricart, JM; Santamaria, C (2023). Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight. Inorganic Chemistry, 62(26), 10100-10109. DOI: 10.1021/acs.inorgchem.3c00043
DOI de l'article: 10.1021/acs.inorgchem.3c00043
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2023
Tipus de publicació: Journal Publications