Photoreactions of the triruthenium cluster Ru3(CO)12 and substituted analogs

Desrosiers, Marc F.; Wink, David A.; TRAUTMAN, R.; Friedman, Alan E.; Ford, Peter C.

doi:10.1021/ja00268a033

Cited by 63 publications

(60 citation statements)

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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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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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“…(Fe(C0)4(PR3) and Fe(C0)3(PR3)2 (3,5, 8, 1 1 -16). Reactions of this type involving R u~( C O )~~ usually afford trinuclear products (17)(18)(19)(20). Photosubstitution of R u~( C O )~~ seems to occur largely from higher energy states whereas photofragmentation involves the lowest excited state (20).…”

mentioning

confidence: 99%

“…Reactions of this type involving R u~( C O )~~ usually afford trinuclear products (17)(18)(19)(20). Photosubstitution of R u~( C O )~~ seems to occur largely from higher energy states whereas photofragmentation involves the lowest excited state (20). The use of the radical anion, sodium diphenylketyl, as a catalyst has recently greatly facilitated the preparation of a wide range of derivatives Ru3(CO),,-,L,, n = 1-4, because the reactions are essentially stoichiometric (21).…”

mentioning

confidence: 99%

Some reactions of ferrocenyl phosphines with M₃(CO)₁₂ (M = Fe, Ru). The structures of Ru₃(CO)₁₁(PFcPh₂) and Ru₃(CO)₁₀{(PPh₂-η-C₅H₄)₂Fe}

Chacon¹,

Cullen²,

Bruce³

et al. 1990

Can. J. Chem.

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Tertiary phosphine substituted metal carbonyl complexes are generally very well known (1) although there have been only a few studies in this area involving ferrocenylphosphines such as PFc,Ph,-,, n = 1-3 (2-8) (FcH = Fe(q-CSH5)2), and 1,l'-disubstituted ferrocene derivatives such as dppf, l,lf-bis(dipheny1phosphino)ferrocene (2,9,10). Phosphine derivatives are generally prepared by direct reaction of the phosphine with the metal carbonyl. Sometimes, and especially in the case of Fe3(C0)12, cluster breakdown is found so that the isolated products are phosphine derivatives of mononuclear carbonyls, e.g. (Fe(C0)4(PR3) and Fe(C0)3(PR3)2 (3,5, 8, 1 1 -16). Reactions of this type involving R u~( C O )~~ usually afford trinuclear products (17)(18)(19)(20). Photosubstitution of R u~( C O )~~ seems to occur largely from higher energy states whereas photofragmentation involves the lowest excited state (20). The use of the radical anion, sodium diphenylketyl, as a catalyst has recently greatly facilitated the preparation of a wide range of derivatives Ru3(CO),,-,L,, n = 1-4, because the reactions are essentially stoichiometric (21). The method is also useful for the synthesis of derivatives of Fe3(C0)12. Salts of the bis(tripheny1phos-phine)iminium ion, ppn+, are also effective catalysts (22).In view of the success in trapping a benzyne fragment on a metal cluster from reactions of arylphosphines with M3(CO),2 'Author to whom correspondence may be addressed.(M = Ru, 0 s ) (23-25) directly or stepwise, we have initiated a study of the corresponding reactions of ferrocenylphosphines in the hope that this will lead to the trapping of a ferrocyne fragment. The present paper describes the synthesis of some derivatives of Fe3(C0)12 and R U~( C O )~~, because of our interest in their pyrolysis products, and the crystal structures of R u~( C O )~ I(PF~Ph2) and Ru3(CO) ,o(p-dppf). The thermal decomposition of R U~( C O )~, , ( P F C P~~)~ to a benzyne complex has been reported (25). Experimental sectionReactions were carried out in a nitrogen atmosphere by using standard Schlenk procedures. Solvents were dried and distilled before use. Separation of products was usually achieved by column chromatography on Florisil or neutral alumina (activity I) by using petroleum ether (35-60°C bp fraction)/diethyl ether mixtures as eluent. I H NMR spectra were recorded from CDC13 solutions by using Bruker WH400 or WP80 and Varian XL300 instruments. Infrared spectra, usually of C6H12 solutions, were run on a Bowman Fourier Transform or a Perkin Elmer 589 spectrometer. Mass spectra were obtained from a Kratos MS 50 instrument; only peaks with high m / e values are listed and electron impact ionization was used unless otherwise stated. Elemental analyses were determined by Mr. P. Borda of the Chemistry Department, University of British Columbia. Melting points were measured by using a Kofler microheating stage and are uncorrected. A Hanovia lOOW lamp (903A-1) was used for UV irradiations. To minimize

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“…The $ s (lim) agrees with the P(OCH 3 ) 3 independent values measured under i.e., 0.22. The value 4.06 for the discrimination ratio compares to 4:1 measured for the unsaturated complex Ru 3 (C0)^ (Desrosiers, 1986).…”

Section: Wavelength (Nm)mentioning

confidence: 53%

“…2 this unusual reaction is promoted by the presence of CO. In earlier studies of the photolytic fragmentation of the triangular cluster Ru 3 (C0)^2 (Desrosiers, 1986), a key step in the proposed mechanism was isomerization leading to heterolytic cleavage of a metal-metal bond with concomitant migration of a terminal CO to a bridging site. Such a transformation would open up a coordination site for a two electron donor such as carbon monoxide.…”

Section: Wavelength (Nm)mentioning

confidence: 99%