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; Jeremie 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, Jeremie Pelletier, Jean-Marie Basset

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21 Scopus citations

Abstract

ABSTRACT: Well-defined single-site silica-supported haf-niaaziridine complex [(≡Si-O-)Hf(η2-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted spe-cies was converted into an 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 ex-tended 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 ex-change with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (η2-NMeNCH2ArCH2) (η1-NMe2)], demonstrating a kind of 2+2 mechanism involving the imine and the imido, proposed reaction mechanism is also supported by DFT calculations.

Original language	English (US)
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 - Sep 4 2018

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10.1021/acscatal.8b01395

https://repository.kaust.edu.sa/bitstream/10754/628705/1/acscatal.8b01395.pdf

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@article{f52fdaedb4fa476ab329649910826ddf,

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

abstract = "ABSTRACT: Well-defined single-site silica-supported haf-niaaziridine complex [(≡Si-O-)Hf(η2-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted spe-cies was converted into an 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 ex-tended 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 ex-change with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (η2-NMeNCH2ArCH2) (η1-NMe2)], demonstrating a kind of 2+2 mechanism involving the imine and the imido, proposed reaction mechanism is also supported by DFT calculations.",

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 Jeremie Pelletier and Jean-Marie Basset",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge 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.",

year = "2018",

month = sep,

day = "4",

doi = "10.1021/acscatal.8b01395",

language = "English (US)",

volume = "8",

pages = "9440--9446",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "10",

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TY - JOUR

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, Jeremie

AU - Basset, Jean-Marie

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge 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.

PY - 2018/9/4

Y1 - 2018/9/4

N2 - ABSTRACT: Well-defined single-site silica-supported haf-niaaziridine complex [(≡Si-O-)Hf(η2-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted spe-cies was converted into an 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 ex-tended 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 ex-change with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (η2-NMeNCH2ArCH2) (η1-NMe2)], demonstrating a kind of 2+2 mechanism involving the imine and the imido, proposed reaction mechanism is also supported by DFT calculations.

AB - ABSTRACT: Well-defined single-site silica-supported haf-niaaziridine complex [(≡Si-O-)Hf(η2-MeNCH2)(η1-NMe2)(η1-HNMe2)] was prepared using surface organometallic chemistry. Upon thermal treatment under high vacuum, the grafted spe-cies was converted into an 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 ex-tended 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 ex-change with N-(4-phenylbenzylidene)benzylamine yielded [(≡Si-O-)Hf (η2-NMeNCH2ArCH2) (η1-NMe2)], demonstrating a kind of 2+2 mechanism involving the imine and the imido, proposed reaction mechanism is also supported by DFT calculations.

UR - http://hdl.handle.net/10754/628705

UR - https://pubs.acs.org/doi/10.1021/acscatal.8b01395

UR - http://www.scopus.com/inward/record.url?scp=85053710300&partnerID=8YFLogxK

U2 - 10.1021/acscatal.8b01395

DO - 10.1021/acscatal.8b01395

M3 - Article

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

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