Journal
INORGANIC CHEMISTRY
Volume 57, Issue 9, Pages 5213-5224Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b00247
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Funding
- National Science Foundation (NSF) [CHE-1465188]
- National Institutes of Health Shared Instrumentation Grant [S10-RR027172]
- Office of Science, Office of Basic Energy Sciences, U.S. Department of Energy [DE-AC02-05CH11231]
- NSF-SAGE IGERT program
- Department of Energy Integrated University Program
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The syntheses of high-valent niobium imido complexes [H2B((Mes)Im)(2)]Nb((NBu)-Bu-t)Cl-2 (2) and [H2B-((Mes)Im)(2)]Nb((NBu)-Bu-t)Me-2 (3) bearing a bis(NHC)borate (NHC = N-heterocyclic carbene) supporting ligand are described. The reaction of the dimethyl complex (3) with excess CO generates an equivalent of acetone, which inserts into a B-H bond of the bis(NHC)borate ligand to form a boryl isopropoxide/niobium(III) dicarbonyl complex (4). This mode of hydroboration reactivity also occurs readily upon the treatment of either 2 or 3 with ketones, aldehydes, and isocyanates. Modification of the bis(carbene) ligand of 3 via the hydroboration of benzophenone produces the dimethylniobium complex [(OCHPh2)(2)B((Mes)Im)(2)]Nb((NBu)-Bu-t)Me-2 (12), which undergoes intramolecular eta(6)-arene coordination upon hydrogenation.
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