Cationic Tantalum Hydrides Catalyze Hydrogenolysis and Alkane Metathesis Reactions of Paraffins and Polyethylene

Gao, Jiaxin; Zhu, Lingchao; Conley, Matthew P.

doi:10.1021/jacs.2c13610

Cationic Tantalum Hydrides Catalyze Hydrogenolysis and Alkane Metathesis Reactions of Paraffins and Polyethylene

Journal Article · Fri Feb 24 00:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c13610· OSTI ID:2544273

Gao, Jiaxin ^[1]; Zhu, Lingchao ^[1]; ^[1]

University of California, Riverside, CA (United States)

Sulfated aluminum oxide (SAO), a high surface area material containing sulfate anions that behave like weakly coordinating anions, reacts with Ta(=CH^tBu)(CH₂^tBu)₃ to form [Ta(CH₂^tBu)₂(O–)₂][SAO] (1). Subsequent treatment with H₂ forms Ta–H⁺ sites supported on SAO that are active in hydrogenolysis and alkane metathesis reactions. In both reactions Ta–H⁺ is more active than related neutral Ta–H sites supported on silica. This reaction chemistry extends to melts of high-density polyethylene (HDPE), where Ta–H⁺ converts 30% of a low molecular weight HDPE (M_n = 2.5 kg mol^–1; D = 3.6) to low molecular weight paraffins under hydrogenolysis conditions. Under alkane metathesis conditions Ta–H⁺ converts this HDPE to a high MW fraction (M_n = 6.2 kDa; D = 2.3) and low molecular weight alkane products (C₁₃–C₃₂). Furthermore, these results show that incorporating charge as a design element in supported d⁰ metal hydrides is a viable strategy to increase the reaction rate in challenging reactions involving reorganization of C–C bonds in alkanes.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022203

OSTI ID:: 2544273

Alternate ID(s):: OSTI ID: 2422085

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 9 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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