MicroED characterization of a robust cationic σ-alkane complex stabilized by the [B(3,5-(SF5)2C6H3)4]− anion, via on-grid solid/gas single-crystal to single-crystal reactivity

Weller, Andrew S.; Doyle, Laurence R.; Thompson, Emily A.; Burnage, Arron L.; Whitwood, Adrian C.; Macgregor, Stuart A.; Jenkins, Huw T.

doi:10.1039/d2dt00335j

Cited by 11 publications

(18 citation statements)

References 41 publications

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“…This is similar to the formation of the cyclotrimerization product 7 in propyne hydrogenation using 1. The 31 P{ 1 H} SSNMR of 11 shows very broad signals at δ 91.4 and ∼δ 71 77 (fwhm ∼2100 Hz, compared with 10 fwhm = 500 Hz) that indicate the formation of an amorphous phase, and consistent with this, SEM analysis of material pre-and post-catalysis shows that significant degradation of the crystal has occurred. Collectively, these data confirm how careful choice of the phosphine substituents is necessary if long catalyst lifetimes are to be maintained, 39 as evident by the fact the t Bu groups in 1 promote the formation of Rh(III) hydride 4 in solid-state.…”

Section: Changing the Smom Catalyst To [Rh-(cy 2 Pch 2 Ch 2 Pcy 2 )(C...supporting

confidence: 53%

Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies

et al. 2023

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The heterogeneous solid−gas reactions of crystals of [Rh(L 2 )(propene)] [BAr F 4 ] (1, L 2 = t Bu 2 PCH 2 CH 2 P t Bu 2 ) with H 2 and propene, 1-butene, propyne, or 1-butyne are explored by gas-phase nuclear magnetic resonance (NMR) spectroscopy under batch conditions at 25 °C. The temporal evolution of the resulting parahydrogen-induced polarization (PHIP) effects measures catalytic flux and thus interrogates the efficiency of catalytic pairwise para-H 2 transfer, speciation changes in the crystalline catalyst at the molecular level, and allows for high-quality singlescan 1 H, 13 C NMR gas-phase spectra for the products to be obtained, as well as 2D-measurements. Complex 4), as probed using EXAFS; meanwhile, a single-crystal of 1 equilibrates NMR silent para-H 2 with its NMR active ortho isomer, contemporaneously converting into 4, and 1 and 4 each convert para-H 2 into ortho-H 2 at different rates. Hydrogenation of propene using 1 and para-H 2 results in very high initial polarization levels in propane (>85%). Strong PHIP was also detected in the hydrogenation products of 1butene, propyne, and 1-butyne. With propyne, a competing cyclotrimerization deactivation process occurs to afford [Rh( t Bu 2 PCH 2 CH 2 P t Bu 2 )(1,3,4-Me 3 C 6 H 3 )][BAr F 4 ], while with 1-butyne, rapid isomerization of 1-butyne occurs to give a butadiene complex, which then reacts with H 2 more slowly to form catalytically active 4. Surprisingly, the high PHIP hydrogenation efficiencies allow hyperpolarization effects to be seen when H 2 is taken directly from a regular cylinder at 25 °C. Finally, changing the chelating phosphine to Cy 2 PCH 2 CH 2 PCy 2 results in initial high polarization efficiencies for propene hydrogenation, but rapid quenching of the catalyst competes to form the zwitterion [Rh(Cy 2 PCH 2 CH 2 PCy 2 ){η 6 -(CF 3 ) 2 (C 6 H 3 )}BAr F 3 ].

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Section: Changing the Smom Catalyst To [Rh-(cy 2 Pch 2 Ch 2 Pcy 2 )(C...supporting

confidence: 53%

Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies

et al. 2023

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“…In contrast to other MOCHA materials with an extended metal chalcogenide core, MicroED has revealed that the synthesized carborane-structured MOCHAs consist of an unprecedented zero-dimensional Cu 4 Se 4 cluster that is representative of the smallest building block of bulk CuSe materials. This work therefore further establishes the utility of MicroED for hybrid material structure elucidation when reaching the limitations of more traditional structural determination methods. − This study furthermore highlights how the use of bulky, organomimetic, boron cluster ligands can lead to the formation of hybrid materials with unique structures and properties. − ,− ,− …”

Section: Discussionmentioning

confidence: 64%

Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

et al. 2022

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Herein, we report the use of sterically invariant carborane-based chalcogenols, containing exopolyhedral B-Se or B-S bonds, as ligands for the formation of photoluminescent copper(I)based metal-organic chalcogenolate assemblies (MOCHAs). We show that precise tuning of the carborane dipole by changing the carborane isomer from meta-to ortho-allows for control over the MOCHA morphology and regulation of the resulting photophysical properties. Furthermore, microcrystal electron diffraction (MicroED) has been demonstrated as a powerful tool for metal chalcogenide structure elucidation. Through the use of MicroED, one of the isolated materials is determined to consist of zero-dimensional Cu 4 (Se-C 2 B 10 H 11 ) 4 clusters with an unprecedented Cu 4 Se 4 geometry.

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“…16 All three measures were consistent with the greater stability of Previously, non-covalent interactions (NCI) plots 22 have highlighted broad areas of dispersive stabilisation between the alkane ligand and the neighbouring [BAr F 4]anions in these -alkane complexes. 11,13,14,17,18 In addition, more localised disk-like features have suggested the presence of C-HF contacts and we have commented on the potential role of such interactions in conferring stability in the solid state. 17 exhibit each end of the range of stabilities seen to date in crystallographically characterised -alkane complexes in the solid state.…”

Section: Faraday Discussion Accepted Manuscriptmentioning

confidence: 90%

A comparison of non-covalent interactions in the crystal structures of two σ-alkane complexes of Rh exhibiting contrasting stabilities in the solid state

2023

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MicroED characterization of a robust cationic σ-alkane complex stabilized by the [B(3,5-(SF₅)₂C₆H₃)₄]⁻ anion, via on-grid solid/gas single-crystal to single-crystal reactivity

Abstract: The thermally and chemically robust σ-alkane complex [Rh(Cy2PCH2CH2PCy2)(norborane)][B(3,5-(SF5)2C6H3)4] is characterized by micro-electron diffraction using on-grid single-crystal to single-crystal reactivity.

Cited by 11 publications

References 41 publications

Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies

Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies

Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

A comparison of non-covalent interactions in the crystal structures of two σ-alkane complexes of Rh exhibiting contrasting stabilities in the solid state

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