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Formation of Bridging Nitride Versus Terminal Oxovanadium Promoted by a Vanadium(II) Macrocyclic Complex
Author(s) -
Jubb Jayne,
Scoles Ludmila,
Jenkins Hilary,
Gambarotta Sandro
Publication year - 1996
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.19960020707
Subject(s) - chemistry , monomer , tetramethylethylenediamine , deoxygenation , vanadium , toluene , medicinal chemistry , cleavage (geology) , stereochemistry , catalysis , inorganic chemistry , organic chemistry , polymer , materials science , fracture (geology) , composite material
The reaction of [VCl 2 (tmeda) 2 ] with the tetralithium salt of octaethylporphyrinogen (oepg)[Li(thf)] 4 initially yielded a monomeric V II complex [(oepg)‐VLi 4 Cl 2 (thf) 4 ] ( 1 ). Treatment of this species with tetramethylethylenediamine afforded a mixture from which [(oepg)‐V(thf) 2 ][Li(tmeda) 2 ].0.5 toluene ( 2 a ) (or 2 b when ethyl is replaced by n Pr) and the unprecedented nitrido‐bridged dimeric species [{oepg)V} 2 (μ‐N)(μ‐Li) 4 ]‐[Li(tmeda) 2 ] ( 3 ) were isolated and characterized. The bridging nitrogen atom probably originated from the cleavage of dinitrogen, since the same reaction carried out under exclusion of N 2 gave [(oepg)VO]‐[Li(tmeda)] 2 ( 4 ), where the oxo atom probably originated from deoxygenation of THF. The connectivity of 1, 2 b, 3 , and 4 was demonstrated by X‐ray analysis.