Redox-Initiated Reactivity of Dinuclear β‑Diketiminatoniobium Imido Complexes

High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N′-bis­(2,4,6-trimethylphenyl)-β-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 yi...

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Published in:Inorganic chemistry 2017-02, Vol.56 (3), p.1626-1637
Main Authors: Kriegel, Benjamin M., Naested, Lara C. E., Nocton, Grégory, Lakshmi, K. V., Lohrey, Trevor D., Bergman, Robert G., Arnold, John
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Chemical Sciences
Inorganic chemistry
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cited_by cdi_FETCH-LOGICAL-a3475-1b655e002edb858c898dc9bb7a9f123c773f25d912eeea0f8d71a7618bf1fb863
cites cdi_FETCH-LOGICAL-a3475-1b655e002edb858c898dc9bb7a9f123c773f25d912eeea0f8d71a7618bf1fb863
container_end_page 1637
container_issue 3
container_start_page 1626
container_title Inorganic chemistry
container_volume 56
creator Kriegel, Benjamin M.
Naested, Lara C. E.
Nocton, Grégory
Lakshmi, K. V.
Lohrey, Trevor D.
Bergman, Robert G.
Arnold, John
description High-valent dichloride and dimethylniobium complexes 1 and 2 bearing tert-butylimido and N,N′-bis­(2,4,6-trimethylphenyl)-β-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.
doi_str_mv 10.1021/acs.inorgchem.6b02735
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title Redox-Initiated Reactivity of Dinuclear β‑Diketiminatoniobium Imido Complexes
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