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Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species.

Pike SD, Weller AS - Philos Trans A Math Phys Eng Sci (2015)

Bottom Line: Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field.Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts.There is a particular focus upon gas-solid reactivity/catalysis and single-crystal-to-single-crystal transformations.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Oxford, Mansfield Road, Oxford UK1 3TA, UK s.pike@imperial.ac.uk.

ABSTRACT
Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas-solid reactivity/catalysis and single-crystal-to-single-crystal transformations.

No MeSH data available.


Related in: MedlinePlus

Trimerization of ethyne using a solid-state catalyst.
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RSTA20140187F21: Trimerization of ethyne using a solid-state catalyst.

Mentions: Solid-state catalysis using well-defined organometallic complexes that are not incorporated into a platform material is a relatively undeveloped field. Bianchini et al. [14] introduced the concept with simple ethene hydrogenation reactions using [(triphos)Ir(H)2(C2H4)][BPh4] at 343 K (scheme 19). The catalyst was active in the solid state, in a mechanism proposed to operate via hydride migration to form an Ir−(C2H5) species, which can react with further H2 followed by reductive elimination of ethane. In solution, the same species was not catalytically active, because a coordinatively saturated dimeric bridging hydride species rapidly forms in the presence of H2 which was inactive for further reactions. Although some of the inactive dimeric species is also formed in the solid-state reaction, it appears to form at a slower rate than in solution. This highlights the ability of the solid state to maintain the integrity of the reactive species by playing a role in protecting them from deactivation pathways that require structural reorganization. The [BPh4]− anions are proposed to create a hydrophobic lattice structure ideal for allowing the passage of small hydrocarbon gases. The catalytic trimerization of ethyne to form benzene was also investigated by Bianchini and co-workers, who showed that a η4-benzene complex (formed itself from a solid–gas reaction) is an active pre-catalyst active at 373 K in the solid state (scheme 20) [55].Scheme 19.


Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species.

Pike SD, Weller AS - Philos Trans A Math Phys Eng Sci (2015)

Trimerization of ethyne using a solid-state catalyst.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4342974&req=5

RSTA20140187F21: Trimerization of ethyne using a solid-state catalyst.
Mentions: Solid-state catalysis using well-defined organometallic complexes that are not incorporated into a platform material is a relatively undeveloped field. Bianchini et al. [14] introduced the concept with simple ethene hydrogenation reactions using [(triphos)Ir(H)2(C2H4)][BPh4] at 343 K (scheme 19). The catalyst was active in the solid state, in a mechanism proposed to operate via hydride migration to form an Ir−(C2H5) species, which can react with further H2 followed by reductive elimination of ethane. In solution, the same species was not catalytically active, because a coordinatively saturated dimeric bridging hydride species rapidly forms in the presence of H2 which was inactive for further reactions. Although some of the inactive dimeric species is also formed in the solid-state reaction, it appears to form at a slower rate than in solution. This highlights the ability of the solid state to maintain the integrity of the reactive species by playing a role in protecting them from deactivation pathways that require structural reorganization. The [BPh4]− anions are proposed to create a hydrophobic lattice structure ideal for allowing the passage of small hydrocarbon gases. The catalytic trimerization of ethyne to form benzene was also investigated by Bianchini and co-workers, who showed that a η4-benzene complex (formed itself from a solid–gas reaction) is an active pre-catalyst active at 373 K in the solid state (scheme 20) [55].Scheme 19.

Bottom Line: Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field.Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts.There is a particular focus upon gas-solid reactivity/catalysis and single-crystal-to-single-crystal transformations.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Oxford, Mansfield Road, Oxford UK1 3TA, UK s.pike@imperial.ac.uk.

ABSTRACT
Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas-solid reactivity/catalysis and single-crystal-to-single-crystal transformations.

No MeSH data available.


Related in: MedlinePlus