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

Research output: Contribution to journalArticlepeer-review

21 Scopus citations


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 languageEnglish (US)
Pages (from-to)9440-9446
Number of pages7
JournalACS Catalysis
Issue number10
StatePublished - Sep 4 2018

Bibliographical 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.


Dive into the research topics of 'Imine Metathesis Catalyzed by a Silica-supported Hafnium Imido Complex'. Together they form a unique fingerprint.

Cite this