ChemInform Abstract: Reactive Cationic Dicyclopentadienylzirconium(IV) Complexes.

Jordan, Richard F.; Dasher, William E.; Echols, Scott

doi:10.1002/chin.198630276

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“…Although the insertion of carbonyl groups into the M−C bonds of early-transition-metal alkyl complexes is precedented, such reactivity occurs more readily for cationic complexes and was not observed with 3. 49,50 The 1 H NMR spectra of 11 and 12 at ambient temperature contain sharp, distinct peaks corresponding to the mesityl methyl groups of the NHC ligand, unlike the spectrum of 3. This suggests that rotation about the N imidazole −C ipso bonds is sufficiently hindered upon carbonyl insertion at the borate moiety such that no spectral broadening is observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Hydroboration Reactivity of Niobium Bis(N-heterocyclic carbene)borate Complexes

et al. 2018

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The syntheses of high-valent niobium imido complexes [HB(Im)]Nb(N Bu)Cl (2) and [HB(Im)]Nb(N Bu)Me (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 [(OCHPh)B(Im)]Nb(N Bu)Me (12), which undergoes intramolecular η-arene coordination upon hydrogenation.

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Section: ■ Results and Discussionmentioning

confidence: 99%