Synthesis and structures of anionic rhenium polyhydride complexes of boron–hydride ligands and their application in catalysis

Donnelly, Liam J.; Parsons, Simon; Morrison, Carole A.; Thomas, Stephen P.; Love, Jason B.

doi:10.1039/d0sc03458d

Cited by 15 publications

(17 citation statements)

References 65 publications

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“…This showed the use of this complex in the catalytic hydroboration of N-heteroaromatic substrates (Scheme 5). 15 The reaction of pyridine with HBpin in the presence of a catalytic amount of 7 resulted in the formation of 1,4-dihydropyridine as a major product (95%) together with a minor amount of a 1,2-addition product (5%). This is one of the rare examples in which a high-oxidation-state transition metal catalyst was employed to hydroborate N-heteroaromatic substrates.…”

Section: Hydroboration Reactionsmentioning

confidence: 99%

“…However, the authors defined it as a sluggish catalyst due to its reduced solubility when compared to the in situ catalyst, generated from the reaction of [N(hexyl) 4 ][ReO 4 ] and HBPin. 15 Subsequently, the reactions of alkynes with Ru-borane/ borate complexes were investigated, which are described here in more detail. Having isolated the σ-borane complex of ruthenium 16 [Cp*(OC)RuH 3 B(mbz)], 8 (mbz = C 7 H 4 NS 2 ) in good yield, it was possible to investigate its reactivity with terminal and internal alkynes (Scheme 6a).…”

Section: Hydroboration Reactionsmentioning

confidence: 99%

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Hydroboration reactions using transition metal borane and borate complexes: an overview

Saha

Ghosh

2022

Dalton Trans.

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Section: Hydroboration Reactionsmentioning

confidence: 99%

Section: Hydroboration Reactionsmentioning

confidence: 99%

Hydroboration reactions using transition metal borane and borate complexes: an overview

Saha

Ghosh

2022

Dalton Trans.

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“…Rhenium complexes and homogeneous counterpart catalysis applications were also discussed. Thus, key chemical questions about heterogeneous catalysts immobilized on solid supports, heterogeneous water‐soluble rhenium nanoparticles, or homogeneous complexes, [20–23] were addressed. We also discuss rhenium‐based hydrogenation reactions in terms of platform molecules and feedstock.…”

Section: Introductionmentioning

confidence: 99%

Rhenium – A Tuneable Player in Tailored Hydrogenation Catalysis

et al. 2021

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Although rhenium may not be the most common choice of active species in catalysis, it has been reported as a highly active and selective catalyst over a wide range of reactions. Its applications include hydrogenation reactions of great relevance in the field of renewable materials and bio‐derived platform molecules, such as valorization of lignin, CO2, and carboxylic acids. Different from several transition metals, rhenium presents oxidation numbers varying from −3 to +7. Such diversity in the coordination chemistry of rhenium is reflected in the variety of known rhenium compounds, since this metal can form stable structures such as ligand‐bridged multinuclear and organometallic compounds as well as inorganic oxides, metal‐organic frameworks, and clusters. The exceptional flexibility in rhenium speciation yields numerous selective catalysts; however, it also makes the characterization of rhenium catalysts challenging, and its influence on the catalytic activity is not trivial. This review will outline the most established rhenium‐based materials used in hydrogenation catalysis and shed some light on the relation of rhenium species to catalyst selectivity based on advanced characterization techniques. Finally, our perspectives on the use of rhenium catalysts to produce value‐added products will be given.

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“…Notably, the optimized dynamic protocol at the 4c-PBE approach was proven to be the most accurate in the prediction of the 1 H NMR hydride chemical shifts of complex 2 , which is consistent with the results obtained for complex 1 . Hence, this is a reliable protocol to calculate the NMR chemical shifts of the terminal and bridging hydrides and has potential utility for the assignment of hydride signals in other challenging metal polyhydrides. − …”

Section: Results and Discussionmentioning

confidence: 99%

First-Principles Calculation of ¹H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics

et al. 2020

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1 H NMR spectroscopy has become an important technique for the characterization of transition-metal hydride complexes, whose metalbound hydrides are often difficult to locate by X-ray diffraction. In this regard, the accurate prediction of 1 H NMR chemical shifts provides a useful, but challenging, strategy to help in the interpretation of the experimental spectra. In this work, we establish a density-functional-theory protocol that includes relativistic, solvent, and dynamic effects at a high level of theory, allowing us to report an accurate and reliable interpretation of 1 H NMR hydride chemical shifts of iridium polyhydride complexes. In particular, we have studied in detail the hydride chemical shifts of the [Ir 6 (IMe) 8 (CO) 2 H 14 ] 2+ complex in order to validate previous assignments. The computed 1 H NMR chemical shifts are strongly dependent on the relativistic treatment, the choice of the DFT exchange−correlation functional, and the conformational dynamics. By combining a fully relativistic four-component electronic-structure treatment with ab initio molecular dynamics, we were able to reliably model both the terminal and bridging hydride chemical shifts and to show that two NMR hydride signals were inversely assigned in the experiment.

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Synthesis and structures of anionic rhenium polyhydride complexes of boron–hydride ligands and their application in catalysis

Abstract: Exhaustive deoxygenation of perrhenate by pinacol borane forms a new Re anion of boron and hydride ligands only that undergoes borane ligand exchange, stoichiometric C–H boration, and catalytic pyridine hydroboration.

Cited by 15 publications

References 65 publications

Hydroboration reactions using transition metal borane and borate complexes: an overview

Hydroboration reactions using transition metal borane and borate complexes: an overview

Rhenium – A Tuneable Player in Tailored Hydrogenation Catalysis

First-Principles Calculation of ¹H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics

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Synthesis and structures of anionic rhenium polyhydride complexes of boron–hydride ligands and their application in catalysis

Abstract: Exhaustive deoxygenation of perrhenate by pinacol borane forms a new Re anion of boron and hydride ligands only that undergoes borane ligand exchange, stoichiometric C–H boration, and catalytic pyridine hydroboration.

Cited by 15 publications

References 65 publications

Hydroboration reactions using transition metal borane and borate complexes: an overview

Hydroboration reactions using transition metal borane and borate complexes: an overview

Rhenium – A Tuneable Player in Tailored Hydrogenation Catalysis

First-Principles Calculation of 1H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics

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First-Principles Calculation of ¹H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics