Highly Selective and Efficient Perdeuteration of n-Pentane via H/D Exchange Catalyzed by a Silica-Supported Hafnium-Iridium Bimetallic Complex.

A Surface OrganoMetallic Chemistry (SOMC) approach is used to prepare a novel hafnium-iridium catalyst immobilized on silica, HfIr/SiO2, featuring well-defined [≡SiOHf(CH2 tBu)2(µ-H)3IrCp*] surface sites. Unlike the monometallic analogous materials Hf/SiO2 and Ir/SiO2, which promote n-pentane deuterogenolysis through C-C bond scission, we demonstrate that under the same experimental conditions (1 bar D2, 250 °C, 3 h, 0.5 mol %), the heterobimetallic catalyst HfIr/SiO2 is highly efficient and selective for the perdeuteration of alkanes with D2, exemplified on n-pentane, without substantial deuterogenolysis (<2 % at 95 % conversion). Furthermore this HfIr/SiO2 catalyst is robust and can be re-used several times without evidence of decomposition. This represents substantial advance in catalytic H/D isotope exchange (HIE) reactions of C(sp3)-H bonds.

Mechanistic investigations via DFT support the cooperative heterobimetallic C-H and O-H bond activation across Ta[double bond, length as m-dash]Ir multiple bonds.

A rare heterobimetallic oxidative addition of X-H (X = C, O) bonds is reported. DFT suggests that steric constraints around the bimetallic core play a critical role to synergistically activate C-H bonds across the two metals and thus explains the exceptional H/D exchange catalytic activity of unhindered surface organometallic Ta/Ir species observed experimentally.

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

A novel heterobimetallic tantalum/iridium hydrido complex, [{Ta(CH2tBu)3}{IrH2(Cp*)}] 1, featuring a very short metal-metal bond, has been isolated through an original alkane elimination route from Ta(CHtBu)(CH2tBu)3 and Cp*IrH4. This molecular precursor has been used to synthesize well-defined silica-supported low-coordinate heterobimetallic hydrido species [≡SiOTa(CH2tBu)2{IrH2(Cp*)}], 5, and [≡SiOTa(CH2tBu)H{IrH2(Cp*)}], 6, using a surface organometallic chemistry (SOMC) approach. The SOMC methodology prevents undesired dimerization as encountered in solution and leading to a tetranuclear species [{Ta(CH2tBu)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, sub-atmospheric D2 pressure) without any additives.