Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides

Wang, Zhuoran; Patnaik, Smita; Eedugurala, Naresh; Manzano, J. Sebastián; Slowing, Igor I.; Kobayashi, Takeshi; Sadow, Aaron D.; Pruski, Marek

doi:10.1021/jacs.9b11606

Title: Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides

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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$$\leftharpoonup$$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. Furthermore, 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.

Authors:

Wang, Zhuoran ^[1];

^[1];

^[2];

^[1];

^[1]

Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Ames Lab., Ames, IA (United States)

Publication Date:: 2020-01-12

Research Org.:: Ames Lab., Ames, IA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1601279

Report Number(s):: IS-J-10158
Journal ID: ISSN 0002-7863

Grant/Contract Number:: AC02-07CH11358

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 142; Journal Issue: 6; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ligands; Ethers; Chemical structure; Catalysts

Citation Formats


                    Wang, Zhuoran, Patnaik, Smita, Eedugurala, Naresh, Manzano, J. Sebastián, Slowing, Igor I., Kobayashi, Takeshi, Sadow, Aaron D., and Pruski, Marek. Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides.  United States: N. p., 2020. 
Web.  doi:10.1021/jacs.9b11606.

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                    Wang, Zhuoran, Patnaik, Smita, Eedugurala, Naresh, Manzano, J. Sebastián, Slowing, Igor I., Kobayashi, Takeshi, Sadow, Aaron D., & Pruski, Marek. Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides.  United States.  https://doi.org/10.1021/jacs.9b11606

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                    Wang, Zhuoran, Patnaik, Smita, Eedugurala, Naresh, Manzano, J. Sebastián, Slowing, Igor I., Kobayashi, Takeshi, Sadow, Aaron D., and Pruski, Marek. Sun .  
"Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides".  United States.  https://doi.org/10.1021/jacs.9b11606.  https://www.osti.gov/servlets/purl/1601279.

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@article{osti_1601279,

  title        = {Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides},

  author       = {Wang, Zhuoran and Patnaik, Smita and Eedugurala, Naresh and Manzano, J. Sebastián and Slowing, Igor I. and Kobayashi, Takeshi and Sadow, Aaron D. and Pruski, Marek},

  abstractNote = {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$\leftharpoonup$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. Furthermore, 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.},

  doi          = {10.1021/jacs.9b11606},

  journal      = {Journal of the American Chemical Society},

  number       = 6,

  volume       = 142,

  place        = {United States},

  year         = {2020},

  month        = {1}

}

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