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Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

  • Identification data

    Identifier: imarina:9321835
    Authors:
    Carbo, JGomez, MHernandez-Prieto, CHernan-Gomez, AMartin, AMena, MPuiggali-Jou, JRicart, JMSantamaria, C
    Abstract:
    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.
  • Others:

    Author, as appears in the article.: Carbo, J; Gomez, M; Hernandez-Prieto, C; Hernan-Gomez, A; Martin, A; Mena, M; Puiggali-Jou, J; Ricart, JM; Santamaria, C
    Department: Química Física i Inorgànica
    URV's Author/s: Carbó Martin, Jorge Juan / Ricart Pla, Jose Manuel
    Keywords: Molecular-orbital methods transition-metals side-on reactivity n-2 unit hydride dinitrogen ligand bond-cleavage augmented basis-sets activation
    Abstract: 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.
    Thematic Areas: 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
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: j.carbo@urv.cat josep.ricart@urv.cat
    Author identifier: 0000-0002-3945-6721 0000-0002-2610-5535
    Record's date: 2024-08-03
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c00043
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Inorganic Chemistry. 62 (26): 10100-10109
    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
    Article's DOI: 10.1021/acs.inorgchem.3c00043
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2023
    Publication Type: Journal Publications
  • Keywords:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Molecular-orbital methods
    transition-metals
    side-on
    reactivity
    n-2 unit
    hydride
    dinitrogen ligand
    bond-cleavage
    augmented basis-sets
    activation
    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
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