(.eta.2-Olefin)tetracarbonylruthenium complexes: photochemical syntheses from dodecacarbonyltriruthenium and quantum yield determinations

Grevels, Friedrich‐Wilhelm; Reuvers, Johannes G. A.; Takats, Josef

doi:10.1021/ja00404a016

Cited by 48 publications

(16 citation statements)

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“…Depending on the level of theory presented in the course, the students can propose reasonable structures on the basis of simple pattern matching to representative spectra (16) or, at more advanced levels, apply group theory to the analysis (9). Once the compounds' structures are appreciated, the Dewar-Chatt-Duncanson (DCD) model (17) can be applied to gain an understanding of the interdependent relationship of the metal-carbonyl and metal-alkene bonding.…”

Section: Resultsmentioning

confidence: 99%

“…The photochemical fragmentation of Ru 3 (CO) 12 can take place under a variety of conditions, ranging from filtered high-intensity light (9,10) to sunlight or conventional fluorescent lighting (12), rendering the experiment quite flexible in terms of the sophistication of equipment required. The UV-vis spectrum of Ru 3 (CO) 12 reveals a single band at the short wavelength extreme of the visible spectrum, centered at 390 nm ( Figure 1).…”

Section: Experimental Backgroundmentioning

confidence: 99%

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Photochemical Synthesis and Ligand Exchange Reactions of Ru(CO)4(n2-alkene) Compounds

2007

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Substituted mononuclear metal carbonyls play a central role in the discussion of organometallic chemistry. In the undergraduate laboratory, these compounds are most often prepared by thermal reaction of the parent binary metal carbonyl with a suitable ligand, L (1). When thermal routes fail, photochemical synthesis is a viable alternative for carbonyl ligand replacement (2), but, with a few notable exceptions (3-7), this approach can often be too technically demanding for the conventional undergraduate laboratory. Even in these instances, the use of sophisticated equipment can be required (4, 5), potentially limiting the applicability of the experiment to only the most well-equipped institutions. Furthermore, the inherent challenges of carrying out synthetic photochemistry on metal carbonyl compounds have thus far limited undergraduate laboratory investigation to the group six metals (Cr, Mo, W) (3-7).Ruthenium pentacarbonyl is thermally unstable and is difficult to handle (8), which often renders thermal reactions inconvenient for the synthesis of Ru(CO) 4 L compounds. However, advantage can be taken of the efficient photochemical metal-metal bond cleavage in Ru 3 (CO) 12 to prepare Ru(CO) 4 (η 2 -alkene) compounds; when a sufficiently labile alkene is used, the latter can serve as [Ru(CO) 4 ] transfer reagents to generate different Ru(CO) 4 L compounds (9, 10). In contrast, thermal reactions of Ru 3 (CO) 12 typically yield ligand-substituted trinuclear clusters (11).From a pedagogic perspective, the students are introduced to the notion that it is not always a metal-carbonyl bond that cleaves in photochemical reactions, but that larger metal clusters can be induced to fragment with useful results. Although Ru 3 (CO) 12 is relatively expensive, 1 the experiments that will be described can be carried out on a scale of only a few mg͞student, with the compounds characterized in situ by IR spectroscopy rather than being isolated. This exposes the students to a common microscale method used in research laboratories when working with reagents that are either very costly or are difficult to prepare in large quantities. We have found that our students appreciate being exposed to the (somewhat novel) prospect of carrying out a photochemical synthesis and being able to learn a great deal about the chemistry of a system without necessarily needing to submit an isolated compound at the conclusion of the experiment. Experimental BackgroundThe photochemical fragmentation of Ru 3 (CO) 12 can take place under a variety of conditions, ranging from filtered high-intensity light (9, 10) to sunlight or conventional fluorescent lighting (12), rendering the experiment quite flexible in terms of the sophistication of equipment required. The UV-vis spectrum of Ru 3 (CO) 12 reveals a single band at the short wavelength extreme of the visible spectrum, centered at 390 nm ( Figure 1). This band has been assigned to a σ → σ* transition in the Ru 3 framework (13), and allows one to understand why a metal-metal bond is cleaved upon photochem...

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Section: Resultsmentioning

confidence: 99%

Section: Experimental Backgroundmentioning

confidence: 99%

Photochemical Synthesis and Ligand Exchange Reactions of Ru(CO)4(n2-alkene) Compounds

2007

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“…Furthermore, this derivative acts as a photocatalyst in photo-activated synthesis, inducing the breaking of selective bonds depending on the excitation wavelength [188,189]. Owing to the high practical and fundamental interest in the metal-metal bond cleavage mechanism, the Ru 3 (CO) 12 metal cluster has been widely investigated, both in solution and in solid matrices, using various spectroscopic methods [189][190][191][192][193][194][195][196][197].…”

Section: (C) the Solution-phase Photochemistry Of The Transition Metamentioning

confidence: 99%

Synchrotron ultrafast techniques for photoactive transition metal complexes

Borfecchia

Garino

Salassa

et al. 2013

Phil. Trans. R. Soc. A.

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In the last decade, the use of time-resolved X-ray techniques has revealed the structure of lightgenerated transient species for a wide range of samples, from small organic molecules to proteins. Time resolutions of the order of 100 ps are typically reached, allowing one to monitor thermally equilibrated excited states and capture their structure as a function of time. This review aims at providing a general overview of the application of timeresolved X-ray solution scattering (TR-XSS) and time-resolved X-ray absorption spectroscopy (TR-XAS), the two techniques prevalently employed in the investigation of light-triggered structural changes of transition metal complexes. In particular, we herein describe the fundamental physical principles for static XSS and XAS and illustrate the theory of timeresolved XSS and XAS together with data acquisition and analysis strategies. Selected pioneering examples of photoactive transition metal complexes studied by TR-XSS and TR-XAS are discussed in depth.

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“…Reaction of I1 with CO to form Ru3-(CO) 13 followed by rapid fragmentation is not unreasonable to contemplate. Relevant rate equations have been rep~rted.~ Reaction 1 does occur in CC14 with a quantum yield ca.…”

Section: Sirmentioning

confidence: 99%