Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes

Heng Liu; Natalia Fridman; Matthias Tamm; Moris S. Eisen

doi:10.1021/acs.organomet.7b00432

Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes

Heng Liu, Natalia Fridman, Matthias Tamm^*, Moris S. Eisen

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

The synthesis of methyl and methoxy substituted benzimidazolin-2-iminato actinide (IV) complexes (1-4), [(Bim^2-MeOPh/MeN)AnN″₃] and [(Bim_5-Me^Dipp/MeN)AnN″₃] (An = U, Th; N″ = N(SiMe₃)₂), was performed by the protonolysis of the actinide metallacycles with the respective neutral benzimidazolin-2-imine ligand precursors. Full characterization, including X-ray diffraction studies for all the complexes, is reported. Despite the high oxophilicity of the actinide metal centers, these complexes displayed extremely high activities in the catalytic addition of aliphatic and aromatic alcohols to carbodiimides, under very mild conditions, providing a facile and highly efficient strategy for the construction of carbon-oxygen bonds. Various kinds of diols and triols can also be used in this intermolecular insertion, representing a large substrate scope for the application of these organoactinide precatalysts.

Original language	English
Pages (from-to)	4600-4610
Number of pages	11
Journal	Organometallics
Volume	36
Issue number	23
DOIs	https://doi.org/10.1021/acs.organomet.7b00432
State	Published - 11 Dec 2017
Externally published	Yes

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title = "Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes",

abstract = "The synthesis of methyl and methoxy substituted benzimidazolin-2-iminato actinide (IV) complexes (1-4), [(Bim2-MeOPh/MeN)AnN″3] and [(Bim5-MeDipp/MeN)AnN″3] (An = U, Th; N″ = N(SiMe3)2), was performed by the protonolysis of the actinide metallacycles with the respective neutral benzimidazolin-2-imine ligand precursors. Full characterization, including X-ray diffraction studies for all the complexes, is reported. Despite the high oxophilicity of the actinide metal centers, these complexes displayed extremely high activities in the catalytic addition of aliphatic and aromatic alcohols to carbodiimides, under very mild conditions, providing a facile and highly efficient strategy for the construction of carbon-oxygen bonds. Various kinds of diols and triols can also be used in this intermolecular insertion, representing a large substrate scope for the application of these organoactinide precatalysts.",

author = "Heng Liu and Natalia Fridman and Matthias Tamm and Eisen, {Moris S.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.organomet.7b00432",

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AU - Liu, Heng

AU - Fridman, Natalia

AU - Tamm, Matthias

AU - Eisen, Moris S.

PY - 2017/12/11

Y1 - 2017/12/11

N2 - The synthesis of methyl and methoxy substituted benzimidazolin-2-iminato actinide (IV) complexes (1-4), [(Bim2-MeOPh/MeN)AnN″3] and [(Bim5-MeDipp/MeN)AnN″3] (An = U, Th; N″ = N(SiMe3)2), was performed by the protonolysis of the actinide metallacycles with the respective neutral benzimidazolin-2-imine ligand precursors. Full characterization, including X-ray diffraction studies for all the complexes, is reported. Despite the high oxophilicity of the actinide metal centers, these complexes displayed extremely high activities in the catalytic addition of aliphatic and aromatic alcohols to carbodiimides, under very mild conditions, providing a facile and highly efficient strategy for the construction of carbon-oxygen bonds. Various kinds of diols and triols can also be used in this intermolecular insertion, representing a large substrate scope for the application of these organoactinide precatalysts.

AB - The synthesis of methyl and methoxy substituted benzimidazolin-2-iminato actinide (IV) complexes (1-4), [(Bim2-MeOPh/MeN)AnN″3] and [(Bim5-MeDipp/MeN)AnN″3] (An = U, Th; N″ = N(SiMe3)2), was performed by the protonolysis of the actinide metallacycles with the respective neutral benzimidazolin-2-imine ligand precursors. Full characterization, including X-ray diffraction studies for all the complexes, is reported. Despite the high oxophilicity of the actinide metal centers, these complexes displayed extremely high activities in the catalytic addition of aliphatic and aromatic alcohols to carbodiimides, under very mild conditions, providing a facile and highly efficient strategy for the construction of carbon-oxygen bonds. Various kinds of diols and triols can also be used in this intermolecular insertion, representing a large substrate scope for the application of these organoactinide precatalysts.

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SN - 0276-7333

VL - 36

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JO - Organometallics

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IS - 23

ER -

Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes

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