Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Banerjee, Sayak; Rodriguez, Jessica; Mais, Marco; Perras, Frédéric A.; Sadow, Aaron D.

doi:10.1002/anie.202511893

Title: Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Journal Article · Tue Jul 08 00:00:00 UTC 2025 · Angewandte Chemie International Edition

DOI: https://doi.org/10.1002/anie.202511893 · OSTI ID:2586712

^[1]; Rodriguez, Jessica ^[1]; Mais, Marco ^[1];

^[1];

^[1]

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

Surface grafted organozirconium catalyzes C─H/Et─Al exchange reactions, involving saturated hydrocarbons and AlEt₃, to afford organoaluminum compounds and ethane. The Zr(O^tBu)₃@SiO₂-Al₂O₃_–700 (1) catalyst contains monopodal ≡SiO─Zr(O^tBu)₃ and only a few residual silanols (<5%). Nonetheless, these silanols are the Achille's heel of 1, providing a pathway for surface and catalyst degradation during catalysis, limiting the alkylaluminum yield and catalyst turnover. Support degradation, involving the cleavage of Si─O bonds by activated surface organometallics, is inhibited by capping silanols with ─SiMe₃. Residual silanols in 1 react with allyltrimethylsilane, as determined by solid-state ¹³C and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and reaction stoichiometry, to form Zr(O^tBu)₃/SiMe₃@SiO₂-Al₂O_3–700 (2), which is resistant to degradation by AlEt₃. C─H alumination of dodecane catalyzed by 2 produces higher yields of the 1-dodecylaluminum product in comparison to 1, and in >95% selectivity. Additionally, methane undergoes 2-catalyzed C─H alumination, providing a route to AlMe₃.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 2586712

Journal Information:: Angewandte Chemie International Edition, Journal Name: Angewandte Chemie International Edition Journal Issue: 36 Vol. 64; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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