Benzimidazolin-2-iminato Hafnium Complexes: Synthesis, Characterization, and Catalytic Addition of Alcohols to Carbodiimides

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

doi:10.1021/acs.organomet.0c00384

Benzimidazolin-2-iminato Hafnium Complexes: Synthesis, Characterization, and Catalytic Addition of Alcohols to Carbodiimides

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

^*Corresponding author for this work

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

12 Scopus citations

Abstract

A series of asymmetric imidazolin-2-iminato and benzimidazolin-2-iminato hafnium(IV) complexes were synthesized and fully characterized including single-crystal X-ray diffraction. The asymmetric imidazolin-2-iminato hafnium complex exhibits a shorter Hf-N bond length as compared with the corresponding benzimidazolin-2-iminato hafnium complex. These complexes were successfully utilized as catalysts for the addition of alcohols to carbodiimides. The synthesis of several active intermediates and kinetics, thermodynamics, and stoichiometric reaction studies allowed us to propose a mechanism for the reaction. The X-ray crystal structure of the monomeric Hf(OtBu)4 is presented.

Original language	English
Pages (from-to)	3021-3033
Number of pages	13
Journal	Organometallics
Volume	39
Issue number	16
DOIs	https://doi.org/10.1021/acs.organomet.0c00384
State	Published - 24 Aug 2020
Externally published	Yes

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title = "Benzimidazolin-2-iminato Hafnium Complexes: Synthesis, Characterization, and Catalytic Addition of Alcohols to Carbodiimides",

abstract = "A series of asymmetric imidazolin-2-iminato and benzimidazolin-2-iminato hafnium(IV) complexes were synthesized and fully characterized including single-crystal X-ray diffraction. The asymmetric imidazolin-2-iminato hafnium complex exhibits a shorter Hf-N bond length as compared with the corresponding benzimidazolin-2-iminato hafnium complex. These complexes were successfully utilized as catalysts for the addition of alcohols to carbodiimides. The synthesis of several active intermediates and kinetics, thermodynamics, and stoichiometric reaction studies allowed us to propose a mechanism for the reaction. The X-ray crystal structure of the monomeric Hf(OtBu)4 is presented.",

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

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T1 - Benzimidazolin-2-iminato Hafnium Complexes

T2 - Synthesis, Characterization, and Catalytic Addition of Alcohols to Carbodiimides

AU - Khononov, Maxim

AU - Liu, Heng

AU - Fridman, Natalia

AU - Tamm, Matthias

AU - Eisen, Moris S.

PY - 2020/8/24

Y1 - 2020/8/24

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AB - A series of asymmetric imidazolin-2-iminato and benzimidazolin-2-iminato hafnium(IV) complexes were synthesized and fully characterized including single-crystal X-ray diffraction. The asymmetric imidazolin-2-iminato hafnium complex exhibits a shorter Hf-N bond length as compared with the corresponding benzimidazolin-2-iminato hafnium complex. These complexes were successfully utilized as catalysts for the addition of alcohols to carbodiimides. The synthesis of several active intermediates and kinetics, thermodynamics, and stoichiometric reaction studies allowed us to propose a mechanism for the reaction. The X-ray crystal structure of the monomeric Hf(OtBu)4 is presented.

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Benzimidazolin-2-iminato Hafnium Complexes: Synthesis, Characterization, and Catalytic Addition of Alcohols to Carbodiimides

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