Skip to Main content Skip to Navigation
Journal articles

Metal–Metal Synergy in Well-Defined Surface Tantalum–Iridium Heterobimetallic Catalysts for H/D Exchange Reactions

Abstract : A novel heterobimetallic tantalum/iridium hydrido complex, [{Ta(CH2 t Bu)3}{IrH2(Cp*)}] 1, featuring a very short metal-metal bond, has been isolated through an original alkane elimination route from Ta(CH t Bu)(CH2 t Bu)3 and Cp*IrH4. This molecular precursor has been used to synthesize well-defined silica-supported low-coordinate heterobime-tallic hydrido species [≡SiOTa(CH2 t Bu)2{IrH2(Cp*)}] 5 and [≡SiOTa(CH2 t Bu)H{IrH2(Cp*)}] 6 using a surface organometallic chemistry approach (SOMC). The SOMC methodology prevents undesired dimerization as encountered in solution and leading to a tetranuclear species [{Ta(CH2 t Bu)2}(Cp*IrH)]2, 4. This approach therefore allows access to unique low-coordinate species not attainable in solution. These original supported Ta/Ir species exhibit drastically enhanced catalytic performances in H/D exchange reactions with respect to (i) monometallic analogues as well as (ii) homogeneous systems. In particular, material 6 promotes the H/D exchange between fluorobenzene and C6D6 or D2 as deuterium sources with excellent productivity (TON up to 1422; TOF up to 23.3 h-1) under mild conditions (25°C, subatmospheric D2 pressure) without any additives.
Document type :
Journal articles
Complete list of metadatas

Cited literature [120 references]  Display  Hide  Download

https://hal.archives-ouvertes.fr/hal-02382262
Contributor : Clément Camp <>
Submitted on : Tuesday, November 10, 2020 - 3:23:32 PM
Last modification on : Saturday, January 23, 2021 - 1:46:04 PM
Long-term archiving on: : Friday, February 12, 2021 - 12:19:05 PM

File

final draft manuscript.pdf
Files produced by the author(s)

Identifiers

Citation

Sébastien Lassalle, Ribal Jabbour, Pauline Schiltz, Pierrick Berruyer, Tanya Todorova, et al.. Metal–Metal Synergy in Well-Defined Surface Tantalum–Iridium Heterobimetallic Catalysts for H/D Exchange Reactions. Journal of the American Chemical Society, American Chemical Society, 2019, ⟨10.1021/jacs.9b08311⟩. ⟨hal-02382262⟩

Share

Metrics

Record views

114

Files downloads

61