Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 34, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202204544
Keywords
Cluster Compounds; Density Functional Calculations; Nitrogen Fixation; Reduction; Titanium
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Funding
- Spanish MCIU [PGC2018-094007-B-I00, PGC2018-093863-B-C21]
- Universidad de Alcala [CCG20/CC-007]
- Spanish Structures of Excellence Maria de Maeztu program [MDM2017-0767]
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By reacting [TiCp*Cl-3] with magnesium, a trinuclear mixed-valence complex is formed, which can react with dinitrogen to produce a diamagnetic compound. The reaction process can potentially be used for cyclic ammonia synthesis under ambient conditions.
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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