Imine Metathesis Catalyzed by a Silica-Supported Hafnium Imido Complex

Maha A. Aljuhani; Samir Barman; Edy Abou-Hamad; Andrei Gurinov; Samy Ould-Chikh; Erjia Guan; Abdesslem Jedidi; Luigi Cavallo; Bruce C. Gates; Jérémie D.A. Pelletier; Jean Marie Basset

doi:10.1021/acscatal.8b01395

Imine Metathesis Catalyzed by a Silica-Supported Hafnium Imido Complex

Maha A. Aljuhani, Samir Barman, Edy Abou-Hamad, Andrei Gurinov, Samy Ould-Chikh, Erjia Guan, Abdesslem Jedidi, Luigi Cavallo^*, Bruce C. Gates, Jérémie D.A. Pelletier, Jean Marie Basset

^*Corresponding author for this work

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

21 Scopus citations

Abstract

The well-defined single-site silica-supported hafniaaziridine complex [(≡Si-O-)Hf(η²,π-MeNCH₂)(η¹-NMe₂)(η¹-HNMe₂)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted species was converted into the unprecedented hafnium imido bis-amido complex [(≡Si-O-)Hf(=NMe)( η¹-NMe₂)]. The surface complexes were characterized by elemental analysis and the following spectroscopic techniques: infrared, solid-state single and multiple quantum NMR, advanced DNP-SENS, and extended X-ray absorption fine structure. [(≡Si-O-)Hf(=NMe)( η¹-NMe₂)] catalyzed imine metathesis under mild conditions, and characterization of the reactivity showed that the imido exchange with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (=NCH₂Ar)( η¹-NMe₂)], demonstrating a kind of 2 + 2 mechanism involving the imine and the imido groups; the proposed reaction mechanism is also supported by DFT calculations.

Original language	English
Pages (from-to)	9440-9446
Number of pages	7
Journal	ACS Catalysis
Volume	8
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.8b01395
State	Published - 5 Oct 2018
Externally published	Yes

Bibliographical note

Funding Information:
The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge the core lab at KAUST for their assistance. The work at the University of California was supported by the U.S. Department of Energy, Basic Energy Sciences, Grant Number DE-FG02-04ER15513. We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities and thank Antonio Aguilar for assistance in using beamline BM30 B.

Publisher Copyright:
Copyright © 2018 American Chemical Society.

Keywords

SOMF
heterogeneous catalysis
imido fragment
imine metathesis
metallaaziridine

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.8b01395

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@article{961b60fd514341a29ed2d791f93725b2,

title = "Imine Metathesis Catalyzed by a Silica-Supported Hafnium Imido Complex",

abstract = "The well-defined single-site silica-supported hafniaaziridine complex [(≡Si-O-)Hf(η2,π-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted species was converted into the unprecedented hafnium imido bis-amido complex [(≡Si-O-)Hf(=NMe)( η1-NMe2)]. The surface complexes were characterized by elemental analysis and the following spectroscopic techniques: infrared, solid-state single and multiple quantum NMR, advanced DNP-SENS, and extended X-ray absorption fine structure. [(≡Si-O-)Hf(=NMe)( η1-NMe2)] catalyzed imine metathesis under mild conditions, and characterization of the reactivity showed that the imido exchange with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (=NCH2Ar)( η1-NMe2)], demonstrating a kind of 2 + 2 mechanism involving the imine and the imido groups; the proposed reaction mechanism is also supported by DFT calculations.",

keywords = "SOMF, heterogeneous catalysis, imido fragment, imine metathesis, metallaaziridine",

author = "Aljuhani, {Maha A.} and Samir Barman and Edy Abou-Hamad and Andrei Gurinov and Samy Ould-Chikh and Erjia Guan and Abdesslem Jedidi and Luigi Cavallo and Gates, {Bruce C.} and Pelletier, {J{\'e}r{\'e}mie D.A.} and Basset, {Jean Marie}",

note = "Funding Information: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge the core lab at KAUST for their assistance. The work at the University of California was supported by the U.S. Department of Energy, Basic Energy Sciences, Grant Number DE-FG02-04ER15513. We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities and thank Antonio Aguilar for assistance in using beamline BM30 B. Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = oct,

day = "5",

doi = "10.1021/acscatal.8b01395",

language = "English",

volume = "8",

pages = "9440--9446",

journal = "ACS Catalysis",

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T1 - Imine Metathesis Catalyzed by a Silica-Supported Hafnium Imido Complex

AU - Aljuhani, Maha A.

AU - Barman, Samir

AU - Abou-Hamad, Edy

AU - Gurinov, Andrei

AU - Ould-Chikh, Samy

AU - Guan, Erjia

AU - Jedidi, Abdesslem

AU - Cavallo, Luigi

AU - Gates, Bruce C.

AU - Pelletier, Jérémie D.A.

AU - Basset, Jean Marie

N1 - Funding Information: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge the core lab at KAUST for their assistance. The work at the University of California was supported by the U.S. Department of Energy, Basic Energy Sciences, Grant Number DE-FG02-04ER15513. We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities and thank Antonio Aguilar for assistance in using beamline BM30 B. Publisher Copyright: Copyright © 2018 American Chemical Society.

PY - 2018/10/5

Y1 - 2018/10/5

N2 - The well-defined single-site silica-supported hafniaaziridine complex [(≡Si-O-)Hf(η2,π-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted species was converted into the unprecedented hafnium imido bis-amido complex [(≡Si-O-)Hf(=NMe)( η1-NMe2)]. The surface complexes were characterized by elemental analysis and the following spectroscopic techniques: infrared, solid-state single and multiple quantum NMR, advanced DNP-SENS, and extended X-ray absorption fine structure. [(≡Si-O-)Hf(=NMe)( η1-NMe2)] catalyzed imine metathesis under mild conditions, and characterization of the reactivity showed that the imido exchange with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (=NCH2Ar)( η1-NMe2)], demonstrating a kind of 2 + 2 mechanism involving the imine and the imido groups; the proposed reaction mechanism is also supported by DFT calculations.

AB - The well-defined single-site silica-supported hafniaaziridine complex [(≡Si-O-)Hf(η2,π-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted species was converted into the unprecedented hafnium imido bis-amido complex [(≡Si-O-)Hf(=NMe)( η1-NMe2)]. The surface complexes were characterized by elemental analysis and the following spectroscopic techniques: infrared, solid-state single and multiple quantum NMR, advanced DNP-SENS, and extended X-ray absorption fine structure. [(≡Si-O-)Hf(=NMe)( η1-NMe2)] catalyzed imine metathesis under mild conditions, and characterization of the reactivity showed that the imido exchange with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (=NCH2Ar)( η1-NMe2)], demonstrating a kind of 2 + 2 mechanism involving the imine and the imido groups; the proposed reaction mechanism is also supported by DFT calculations.

KW - SOMF

KW - heterogeneous catalysis

KW - imido fragment

KW - imine metathesis

KW - metallaaziridine

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DO - 10.1021/acscatal.8b01395

M3 - Article

AN - SCOPUS:85053710300

SN - 2155-5435

VL - 8

SP - 9440

EP - 9446

JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

Imine Metathesis Catalyzed by a Silica-Supported Hafnium Imido Complex

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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