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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.


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Solid–gas reactivity of a dimeric species to afford monomeric complexes.
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RSTA20140187F3: Solid–gas reactivity of a dimeric species to afford monomeric complexes.

Mentions: An interesting case of ligand displacement, in as much as that cleavage of a dimer is occurring in the solid state, comes from the reaction shown in scheme 2 in which Werner and co-workers [45] reported that addition of CO or ethene to a chloride-bridged Rh(I) dimer resulted in the generation of monomeric species, where two dative Rh–Cl bonds had been cleaved by CO or ethene. Other examples of ligand of displacement in the solid state have been reported. Werner and co-workers reported that addition of CO to a Rh-complex that contains a hemilabile [46,47] phosphine–ether ligand results in displacement of one Rh–ether linkage, whereas a dicarbonyl will form in the analogous solution-phase reaction (scheme 3) [45]. Addition of CO to Rh(PPh3)3(OAr) (e.g. Ar=C6Cl5) in the solid state results in an intermediate, tentatively described as five-coordinate Rh(PPh3)3(OAr)(CO), from which washing of the solid with ether removes PPh3 to afford trans-Rh(PPh3)2(OAr)(CO) [48]. Related five-coordinate species can be isolated from addition of CO in the solid state to square planar complexes such as [Ir(COD)(PPh3)(PhCN)][ClO4] to give, for example, [Ir(COD)(PPh3)(CO)2][ClO4] via loss of PhCN [49]. Milstein and co-workers [50] have shown that CO can bind reversibly to a 16-electron Rh(I) nitrosyl pincer complex, in which an equilibrium is established between a five-coordinate, CO-bound, and four-coordinate, CO-free, complex. Concomitant with this addition of CO is the change in NO binding mode from linear to bent, as measured by infrared (IR) spectroscopy.Scheme 2.


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)

Solid–gas reactivity of a dimeric species to afford monomeric complexes.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

RSTA20140187F3: Solid–gas reactivity of a dimeric species to afford monomeric complexes.
Mentions: An interesting case of ligand displacement, in as much as that cleavage of a dimer is occurring in the solid state, comes from the reaction shown in scheme 2 in which Werner and co-workers [45] reported that addition of CO or ethene to a chloride-bridged Rh(I) dimer resulted in the generation of monomeric species, where two dative Rh–Cl bonds had been cleaved by CO or ethene. Other examples of ligand of displacement in the solid state have been reported. Werner and co-workers reported that addition of CO to a Rh-complex that contains a hemilabile [46,47] phosphine–ether ligand results in displacement of one Rh–ether linkage, whereas a dicarbonyl will form in the analogous solution-phase reaction (scheme 3) [45]. Addition of CO to Rh(PPh3)3(OAr) (e.g. Ar=C6Cl5) in the solid state results in an intermediate, tentatively described as five-coordinate Rh(PPh3)3(OAr)(CO), from which washing of the solid with ether removes PPh3 to afford trans-Rh(PPh3)2(OAr)(CO) [48]. Related five-coordinate species can be isolated from addition of CO in the solid state to square planar complexes such as [Ir(COD)(PPh3)(PhCN)][ClO4] to give, for example, [Ir(COD)(PPh3)(CO)2][ClO4] via loss of PhCN [49]. Milstein and co-workers [50] have shown that CO can bind reversibly to a 16-electron Rh(I) nitrosyl pincer complex, in which an equilibrium is established between a five-coordinate, CO-bound, and four-coordinate, CO-free, complex. Concomitant with this addition of CO is the change in NO binding mode from linear to bent, as measured by infrared (IR) spectroscopy.Scheme 2.

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