Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides
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Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.
For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.
The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
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The Department of Chemistry was founded in 1880.
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1880-present
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- College of Liberal Arts and Sciences (parent college)
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Abstract
Single-site organolanthanum complexes supported on mesoporous silica nanoparticles, La{C(SiHMe2)3}n@MSNs, catalyze the ring-opening hydroboration reaction of aliphatic and styrenic epoxides with pinacolborane (HBpin). The surface-bound complexes, synthesized by reaction of the homoleptic tris(alkyl)lanthanum La{C(SiHMe2)3}3 and SBA-type MSN treated at 700 °C (MSN700), are mostly monopodal ≡SiO—La{C(SiHMe2)3}2 and contain an average of one bridging La↼H—Si per alkyl ligand. This structure was established through a combination of solid-state NMR (SSNMR) experiments, including J-resolved SiH coupling and quantitative 29Si measurements, diffuse reflectance IR, and elemental analysis. These rigorous analyses also established that grafting reactions in pentane provide a preponderance of ≡SiO—La{C(SiHMe2)3}2 sites and are superior to those in benzene and THF, and that grafting onto MSN treated at 550 °C (MSN550) results in a mixture of surface species. The single-site supported catalysts are more selective and in most cases more active than the homogeneous analogue, allow easy purification of products from the catalyst, are strongly resistant to leaching into solution phase, and may be recycled for reuse at least five times. After reaction of La{C(SiHMe2)3}n@MSN and HBpin, species including ≡SiO—La{C(SiHMe2)3}(H2Bpin) and ≡SiO—La{C(SiHMe2)3}{κ2–pinB–O(CMe2)2OBH3} are identified by detailed 1D and 2D 11B SSNMR experiments.
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This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/jacs.9b11606. Posted with permission.