Redox-Initiated Reactivity of Dinuclear ß-Diketiminatoniobium Imido Complexes.
Inorg Chem
; 56(3): 1626-1637, 2017 Feb 06.
Article
em En
| MEDLINE
| ID: mdl-28098983
ABSTRACT
High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N'-bis(2,4,6-trimethylphenyl)-ß-diketiminate (BDIAr) ligands were prepared. The dimethyl complex reacted with dihydrogen to release methane and generate the hydride-bridged diniobium(IV) complex 3 in high yield. One-electron oxidation of 3 with silver salts resulted in the release of dihydrogen and conversion to a mixed-valent NbIII-NbIV complex, 4, that displayed a frozen-solution X-band electron paramagnetic resonance signal consistent with a slight dissymmetry between the two Nb centers. Spectroscopic and computational analysis supported the presence of Nb-Nb σ-bonding interactions in both 3 and 4. Finally, one-electron reduction of 4 resulted in conversion to the highly dissymmetric NbV-NbV dimer 5 that formed from the reductive C-N bond cleavage of one of the BDIAr supporting ligands.
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MEDLINE
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En
Ano de publicação:
2017
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Article