Isolable Silylene Ligands Can Boost Efficiencies and Selectivities in Metal‐Mediated Catalysis

Zhou, Yu‐Peng; Drieß, Matthias

doi:10.1002/ange.201811088

“…As a specific projection for future research, silicon-donor ligands are well established in homogeneous catalysis in the form of silyls and silylenes, and their diverse structural and electronic properties suggest that they should also have considerable scope for incorporation into the design of SMMs in a manner reminiscent of alkyl and carbene ligands. 139 Main group chemistry has demonstrated a remarkable ability to reinvent itself in ways that are genuinely paradigm-shifting. The biggest impact of this has undoubtedly been in the context of synthetic chemistry, with the concepts of main group elements as transition metals 140 and frustrated Lewis pairs (FLPs) 141 proving to be particularly influential.…”

Section: Discussionmentioning

confidence: 99%

Main Group Chemistry at the Interface with Molecular Magnetism

Guo

¹

,

Bar

²

,

Layfield

³

2019

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Innovative synthetic coordination and, increasingly, organometallic chemistry are at the heart of advances in molecular magnetism. Smart ligand design is essential for implementing controlled modifications to the electronic structure and magnetic properties of transition metal and f-element compounds, and many important recent developments use nontraditional ligands based on low-coordinate main group elements to drive the field forward. This review charts progress in molecular magnetism from the perspective of ligands in which the donor atoms range from low-coordinate 2p elementsparticularly carbon but also boron and nitrogento the heavier p-block elements such as phosphorus, arsenic, antimony, and even bismuth. Emphasis is placed on the role played by novel main group ligands in addressing magnetic anisotropy of transition metal and f-element compounds, which underpins the development of single-molecule magnets (SMMs), a family of magnetic materials that can retain magnetization in the absence of a magnetic field below a blocking temperature. Nontraditional p-block donor atoms, with their relatively diffuse valence orbitals and more diverse bonding characteristics, also introduce scope for tuning the spin−orbit coupling properties and metal−ligand covalency in molecular magnets, which has implications in areas such as magnetic exchange coupling and spin crossover phenomena. The chemistry encompasses transition metals, lanthanides, and actinides and describes recently discovered molecular magnets that can be regarded, currently, as defining the state of the art. This review identifies that main group chemistry at the interface molecular magnetism is an area with huge potential to deliver new types of molecular magnets with previously unseen properties and applications.

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“…To overcome this limitation base-stabilized tetrylenes have been explored and their complexes have found relevance in catalysis. [26][27][28][29] Nonetheless, quenching their Z-type character by inter-or intramolecular bases hampers their potential to actively cooperate with the transition metal in bond activation processes.…”

mentioning

confidence: 99%

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Bajo¹,

Alcaide²,

López-Serrano³

et al. 2021

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0

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Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.

show abstract

“…To overcome this limitation base-stabilized tetrylenes have been explored and their complexes have found relevance in catalysis. [26][27][28][29] Nonetheless, quenching their Z-type character by inter-or intramolecular bases hampers their potential to actively cooperate with the transition metal in bond activation processes.…”

mentioning

confidence: 99%

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Bajo¹,

Alcaide²,

López-Serrano³

et al. 2021

Preprint

0

View full text Add to dashboard Cite

Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.

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Isolable Silylene Ligands Can Boost Efficiencies and Selectivities in Metal‐Mediated Catalysis

Cited by 40 publications

References 95 publications

Main Group Chemistry at the Interface with Molecular Magnetism

Main Group Chemistry at the Interface with Molecular Magnetism

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

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