Dalton perspectives. The generation and reactivity of versatile ruthenium carbonyl organometallic intermediates by cluster photochemistry

Leadbeater, Nicholas E.

doi:10.1039/dt9950002923

Cited by 28 publications

(23 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Triiron dodecacarbonyl (Fe 3 (CO) 12 ) exists in the solution phase primarily as an isomer containing all terminal CO ligands, with a minor fraction of a second isomer containing two bridging CO ligands also present (see Figure 6). [73][74][75] The fraction of the bridged isomer has been estimated at 5-10% of the total population of Fe 3 (CO) 12 mole-cules, though the ratio of isomers varies with the choice of solvent.…”

Section: Fe3(co)12mentioning

confidence: 99%

“…Turning next to the ruthenium congener, triruthenium dodecacarbonyl (Ru 3 (CO) 12 ) is characterized by an allterminal CO structure, with a triangular skeleton of three Ru atoms each bearing four terminal CO ligands (similar to the major isomer of Fe 3 (CO) 12 ). 81,82 Only this one isomer is present in solutions of Ru 3 (CO) 12 .…”

Section: Ru3(co)12mentioning

confidence: 99%

“…More recent studies using time-resolved X-ray experiments appear to have uncovered an additional long-lived photoproduct in the photochemistry of Ru 3 (CO) 12 , which is the di-carbonyl loss species Ru 3 (CO) 10 . 87,88 This represents a rare example of di-carbonyl loss occurring following a single photon absorption event in the solution phase.…”

Section: Ru3(co)12mentioning

confidence: 99%

“…However, it turns out that much of the behavior of the three group 8 metal carbonyl trimers is quite nuanced. Fe 3 (CO) 12 , for example, is the only cluster for which products arising from fragmentation of the M 3 skeleton were observed. As was discussed in an earlier publication, photochemical fragmentation of the iron cluster likely proceeds more readily due to the weaker Fe-Fe bonds holding together the Fe 3 skeleton, relative to those of the ruthenium and osmium congeners.…”

Section: Comparison Of Reactivitymentioning

confidence: 99%

“…A number of other excellent reviews and books on this and related topics have been published over the years, and we refer interested readers to some of these publications for additional insight. [10][11][12][13][14][15][16] 2. Photochemistry of Metal Carbonyl Dimers…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Primary photochemical dynamics of metal carbonyl dimers and clusters in solution: Insights into the results of metal–metal bond cleavage from ultrafast spectroscopic studies

Lomont

Harris

2015

Inorganica Chimica Acta

View full text Add to dashboard Cite

Supporting Information PlaceholderABSTRACT: Metal carbonyl dimers and clusters constitute a diverse class of organometallic reagents and catalysts. The photochemistry of these complexes is a topic of significant and long-standing interest, as preparative-scale photolyses constitute many of the most synthetically powerful reactions in organometallic chemistry. The metal-metal bonding present in dimers and clusters is varied and significantly influences their overall reactivity. In this review we discuss the primary photochemical dynamics of transition metal carbonyl metal dimers and clusters, with a focus on the changes in metal-metal bonding that occur upon visible and/or ultraviolet photochemical excitation. The bulk of the results discussed here were obtained using ultrafast time-resolved infrared spectroscopy, a technique with high structural sensitivity afforded by the carbonyl reporter ligands of the complexes studied. Picosecond time resolution allows detailed monitoring of the photochemical reaction dynamics, including observation of initially excited complexes and short-lived transient metal-metal bond cleavage intermediates, as well as formation of the longer-lived, yet reactive, intermediates responsible for reactivity occurring on diffusion-limited time scales and beyond.

show abstract

Section: Fe3(co)12mentioning

confidence: 99%

Section: Ru3(co)12mentioning

confidence: 99%

Section: Ru3(co)12mentioning

confidence: 99%

Section: Comparison Of Reactivitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Primary photochemical dynamics of metal carbonyl dimers and clusters in solution: Insights into the results of metal–metal bond cleavage from ultrafast spectroscopic studies

Lomont

Harris

2015

Inorganica Chimica Acta

View full text Add to dashboard Cite

show abstract

Low‐Lying Excited States and Primary Photoproducts of [Os₃(CO)₁₀(s‐cis‐L)] (L=Cyclohexa‐1,3‐diene, Buta‐1,3‐diene)] Clusters Studied by Picosecond Time‐Resolved UV/Vis and IR Spectroscopy and by Density Functional Theory

Vergeer

Matousek

Towrie

et al. 2004

Chemistry A European J

View full text Add to dashboard Cite

Combined picosecond transient absorption and time-resolved infrared studies were performed, aimed at characterising low-lying excited states of the cluster [Os(3)(CO)(10)(s-cis-L)] (L=cyclohexa-1,3-diene, 1) and monitoring the formation of its photoproducts. Theoretical (DFT and TD-DFT) calculations on the closely related cluster with L=buta-1,3-diene (2') have revealed that the low-lying electronic transitions of these [Os(3)(CO)(10)(s-cis-1,3-diene)] clusters have a predominant sigma(core)pi*(CO) character. From the lowest sigmapi* excited state, cluster 1 undergoes fast Os-Os(1,3-diene) bond cleavage (tau=3.3 ps) resulting in the formation of a coordinatively unsaturated primary photoproduct (1 a) with a single CO bridge. A new insight into the structure of the transient has been obtained by DFT calculations. The cleaved Os-Os(1,3-diene) bond is bridged by the donor 1,3-diene ligand, compensating for the electron deficiency at the neighbouring Os centre. Because of the unequal distribution of the electron density in transient 1 a, a second CO bridge is formed in 20 ps in the photoproduct [Os(3)(CO)(8)(micro-CO)(2)(cyclohexa-1,3-diene)] (1 b). The latter compound, absorbing strongly around 630 nm, mainly regenerates the parent cluster with a lifetime of about 100 ns in hexane. Its structure, as suggested by the DFT calculations, again contains the 1,3-diene ligand coordinated in a bridging fashion. Photoproduct 1 b can therefore be assigned as a high-energy coordination isomer of the parent cluster with all Os-Os bonds bridged.

show abstract

Inorganic Photochemistry

Weinstein¹

2013

Applied Photochemistry

View full text Add to dashboard Cite

Dalton perspectives. The generation and reactivity of versatile ruthenium carbonyl organometallic intermediates by cluster photochemistry

Cited by 28 publications

References 30 publications

Primary photochemical dynamics of metal carbonyl dimers and clusters in solution: Insights into the results of metal–metal bond cleavage from ultrafast spectroscopic studies

Primary photochemical dynamics of metal carbonyl dimers and clusters in solution: Insights into the results of metal–metal bond cleavage from ultrafast spectroscopic studies

Low‐Lying Excited States and Primary Photoproducts of [Os₃(CO)₁₀(s‐cis‐L)] (L=Cyclohexa‐1,3‐diene, Buta‐1,3‐diene)] Clusters Studied by Picosecond Time‐Resolved UV/Vis and IR Spectroscopy and by Density Functional Theory

Inorganic Photochemistry

Contact Info

Product

Resources

About

Dalton perspectives. The generation and reactivity of versatile ruthenium carbonyl organometallic intermediates by cluster photochemistry

Cited by 28 publications

References 30 publications

Primary photochemical dynamics of metal carbonyl dimers and clusters in solution: Insights into the results of metal–metal bond cleavage from ultrafast spectroscopic studies

Primary photochemical dynamics of metal carbonyl dimers and clusters in solution: Insights into the results of metal–metal bond cleavage from ultrafast spectroscopic studies

Low‐Lying Excited States and Primary Photoproducts of [Os3(CO)10(s‐cis‐L)] (L=Cyclohexa‐1,3‐diene, Buta‐1,3‐diene)] Clusters Studied by Picosecond Time‐Resolved UV/Vis and IR Spectroscopy and by Density Functional Theory

Inorganic Photochemistry

Contact Info

Product

Resources

About

Low‐Lying Excited States and Primary Photoproducts of [Os₃(CO)₁₀(s‐cis‐L)] (L=Cyclohexa‐1,3‐diene, Buta‐1,3‐diene)] Clusters Studied by Picosecond Time‐Resolved UV/Vis and IR Spectroscopy and by Density Functional Theory