Dinitrogen Binding at a Trititanium Chloride Complex and Its Conversion to Ammonia under Ambient Conditions.
Authors
Horno Martín, Estefanía del; Jover, Jesús; Mena Montoro, Miguel; Pérez Redondo, Adrián; Yélamos Sánchez, CarlosIdentifiers
Permanent link (URI): http://hdl.handle.net/10017/53090DOI: 10.1002/anie.202204544
ISSN: 0570-0833
Date
2022-06-24Funders
Ministerio de Ciencia, Innovación y Universidades, Universidad de Alcalá, Spanish Structures of Excellence María de Maeztu
Bibliographic citation
Angewandte Chemie - International Edition in English, 2022, v. 61, n. 34, p. E202204544
Keywords
Cluster compounds
Density functional calculations
Nitrogen fixation
reduction
titanium
Project
CCG20/CC-007, MDM-2017-0767
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-094007-B-I00/ES/SISTEMAS MOLECULARES MULTIMETALICOS PARA LA ACTIVACION Y FUNCIONALIZACION DE DINITROGENO/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-093863-B-C21/ES/ESTRUCTURA ELECTRONICA Y PROPIEDADES DE MOLECULAS Y SOLIDOS/
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Rights
Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
Access rights
info:eu-repo/semantics/openAccess
Abstract
Reaction of [TiCp*Cl-3] (Cp*=eta(5)-C5Me5) with one equivalent of magnesium in tetrahydrofuran at room temperature affords the paramagnetic trinuclear complex [{TiCp*(mu-Cl)}(3)(mu(3)-Cl)], which reacts with dinitrogen under ambient conditions to give the diamagnetic derivative [{TiCp*(mu-Cl)}(3)(mu(3)-eta(1) : eta(2) : eta(2)-N-2)] and the titanium(III) dimer [{TiCp*Cl(mu-Cl)}(2)]. The structure of the trinuclear mixed-valence complexes has been studied by experimental and theoretical methods and the latter compound represents the first well-defined example of the mu(3)-eta(1) : eta(2) : eta(2) coordination mode of the dinitrogen molecule. The reaction of [{TiCp*(mu-Cl)}(3)(mu(3)-eta(1) : eta(2) : eta(2)-N-2)] with excess HCl in tetrahydrofuran results in clean NH4Cl formation with regeneration of the starting material [TiCp*Cl-3]. Therefore, a cyclic ammonia synthesis under ambient conditions can be envisioned by alternating N-2/HCl atmospheres in a [TiCp*Cl-3]/Mg(excess) reaction mixture in tetrahydrofuran.
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