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Cleavage of Dinitrogen from Forming Gas by a Titanium Molecular System under Ambient Conditions
Author(s) -
GonzálezMoreiras Mariano,
Mena Miguel,
PérezRedondo Adrián,
Yélamos Carlos
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201700152
Subject(s) - chemistry , medicinal chemistry , protonation , chloroform , cubane , titanium , stereochemistry , crystallography , crystal structure , organic chemistry , ion
Simple exposure of a hexane solution of [TiCp*Me 3 ] (Cp*=η 5 ‐C 5 Me 5 ) to an atmosphere of commercially available and inexpensive forming gas (H 2 /N 2 mixture, 13.5–16.5 % of H 2 ) at room temperature leads to the methylidene–methylidyne–nitrido cube‐type complex [(TiCp*) 4 (μ 3 ‐CH)(μ 3 ‐CH 2 )(μ 3 ‐N) 2 ] via dinitrogen cleavage. This paramagnetic compound reacts with [D 1 ]chloroform to give the titanium(IV) methylidyne–nitrido species [(TiCp*) 4 (μ 3 ‐CH) 2 (μ 3 ‐N) 2 ], whereas its one‐electron oxidation with AgOTf or [Fe(η 5 ‐C 5 H 5 ) 2 ](OTf) (OTf=O 3 SCF 3 ) yields the diamagnetic ionic derivative [(TiCp*) 4 (μ 3 ‐CH)(μ 3 ‐CH 2 )(μ 3 ‐N) 2 ](OTf). The μ 3 ‐nitrido ligands of the methylidyne–nitrido cubane complex can be protonated with [LutH](OTf) (Lut=2,6‐lutidine) or hydrogenated with NH 3 ⋅ BH 3 to afford μ 3 ‐NH imido moieties.