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)|
|Number of pages||7|
|State||Published - Sep 4 2018|
Bibliographical noteKAUST 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.