Catalytic regeneration of metal-hydrides from their corresponding metal-alkoxides <i>via</i> the hydroboration of carbonates to obtain methanol and diols

Eisen, Moris S.; Deka, Hemanta; Caporaso, Lucia; Ritacco, Ida

doi:10.1039/d3sc01700a

Chem. Sci.

2023

DOI: 10.1039/d3sc01700a

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Catalytic regeneration of metal-hydrides from their corresponding metal-alkoxides via the hydroboration of carbonates to obtain methanol and diols

Moris S. Eisen¹,

Hemanta Deka²,

Lucia Caporaso³

et al.

Abstract: Thorium complexes decorated with 5-, 6-, and 7-membered N-heterocyclic iminato ligands containing mesityl wingtip substitutions have been synthesized and fully characterized. These complexes were found to be efficient in the...

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Against All Odds, Uranium and Thorium Iminato Complexes Enable the Cleavage of C═O Bonds in Isocyanates

Makarov,

Ritacco,

Fridman

et al. 2023

ACS Catal.

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The catalytic activity of actinide-based catalysts is presented herein for the hydroboration and deoxygenation of isocyanates with pinacolborane (HBpin). A modified class of ligand systems possessing a five-membered ring core constructing the N-heterocyclic iminato moiety is introduced. All actinide complexes showed very good catalytic activities under mild conditions, with low catalyst loadings achieving almost quantitative yields. A wide number of isocyanates were studied including aliphatic isocyanates, aromatic isocyanates, and diisocyanates yielding to the corresponding borylated N-methyl amines and the borylated formamides, which are easily hydrolyzed toward the free amines and formamides. These organoactinide catalysts exhibited a great functional group tolerance toward methoxy, amido, and halides. The reaction selectivity was thoroughly investigated and exhibited a very good selectivity toward the isocyanate functionality having double or triple unsaturated C−C bonds. Kinetic studies were performed in order to establish the rate order dependency on the concentrations of the organoactinide complex, HBpin, and isocyanate. A proposed mechanism is presented based on experiments affording a more comprehensive understanding of the experimental activity trends and reinforced by the stoichiometric reaction studies, thermodynamic measurements, deuterium-labeling experiments, and theoretical DFT calculations.

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Against All Odds, Uranium and Thorium Iminato Complexes Enable the Cleavage of C═O Bonds in Isocyanates

Makarov,

Ritacco,

Fridman

et al. 2023

ACS Catal.

Self Cite

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Catalytic regeneration of metal-hydrides from their corresponding metal-alkoxides via the hydroboration of carbonates to obtain methanol and diols

Abstract: Thorium complexes decorated with 5-, 6-, and 7-membered N-heterocyclic iminato ligands containing mesityl wingtip substitutions have been synthesized and fully characterized. These complexes were found to be efficient in the...

Cited by 1 publication

References 79 publications

Against All Odds, Uranium and Thorium Iminato Complexes Enable the Cleavage of C═O Bonds in Isocyanates

Against All Odds, Uranium and Thorium Iminato Complexes Enable the Cleavage of C═O Bonds in Isocyanates

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