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. 2025 Sep 1;64(36):e202511893.
doi: 10.1002/anie.202511893. Epub 2025 Jul 30.

Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Sayak Banerjee  1   2 , Jessica Rodriguez  2 , Marco Mais  2 , Frédéric A Perras  1   2 , Aaron D Sadow  1   2
Affiliations

Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Sayak Banerjee et al. Angew Chem Int Ed Engl. .

Abstract

Surface grafted organozirconium catalyzes C─H/Et─Al exchange reactions, involving saturated hydrocarbons and AlEt3, to afford organoaluminum compounds and ethane. The Zr(OtBu)3@SiO2-Al2O3-700 (1) catalyst contains monopodal ≡SiO─Zr(OtBu)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(OtBu)3/SiMe3@SiO2-Al2O3-700 (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.

Keywords: CH activation; Catalysis; Hydrocarbon alumination; Methane functionalization; Surface organometallic chemistry.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
DNP‐enhanced 13C (a) and 29Si (b) CPMAS NMR spectra measured for SiO2‐Al2O3–700 (i) and Zr(O t Bu)3@SiO2‐Al2O3–700 (ii) materials treated with 60 equiv of AlEt3 and/or allyltrimethylsilane, as indicated. In (a) an asterisk denotes the presence of aliphatic impurities. SiO2‐Al2O3–700 and AlEt3 or SiMe3@SiO2‐Al2O3–700 and AlEt3 were heated at 150 °C in dodecane prior to analysis.
Figure 2
Figure 2
Decreasing or increasing turnovers for dodecylaluminum formation with increasing AlEt3 equivalents using catalysts 1 (red patterned bars) or 2 (blue filled bars), respectively.
Scheme 1
Scheme 1
Selective silylation of residual surface OH in 1 in the presence of grafted tert‐butoxyzirconium species to form 2.
Figure 3
Figure 3
DRIFTS of SiO2‐Al2O3–700 (black continuous), 1 (grey dashed) and 2 (blue dotted), normalized to the silicon framework signal at 1610 cm−1.
See this image and copyright information in PMC

References

    1. Ziegler K., in Adv. Organomet. Chem., Vol. 6 (Eds.: Stone F. G. A., West R.), Academic Press, Cambridge: 1968, pp. 1–17.
    1. Noweck K., Grafahrend W., in “Fatty Alcohols” Ullmann's Encyclopedia of Industrial Chemistry, Wiley‐VCH Online, 2006, 10.1002/14356007.a10_277.pub2. - DOI
    1. Xu S., Negishi E.‐i., Acc. Chem. Res. 2016, 49, 2158–2168. - PubMed
    1. Hartwig J. F., Acc. Chem. Res. 2012, 45, 864–873. - PubMed
    1. Smith K. T., Berritt S., González‐Moreiras M., Ahn S., Smith M. R., Baik M.‐H., Mindiola D. J., Science 2016, 351, 1424. - PMC - PubMed

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