Imine Metathesis Catalyzed by a Silica-supported Hafnium Imido Complex
AuthorsAljuhani, Maha A.
Gates, Bruce C.
KAUST DepartmentChemical Science Program
Imaging and Characterization Core Lab
KAUST Catalysis Center (KCC)
Physical Sciences and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/628705
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AbstractABSTRACT: 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.
CitationAljuhani MA, Barman S, Abou-Hamad E, Gurinov AA, Ould-Chikh S, et al. (2018) Imine Metathesis Catalyzed by a Silica-supported Hafnium Imido Complex. ACS Catalysis. Available: http://dx.doi.org/10.1021/acscatal.8b01395.
SponsorsThe 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.
PublisherAmerican Chemical Society (ACS)