NDLI: Electrochemical and Photochemical Conversion of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] into [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$

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Toward the Experimental Structure Determination of Larger Molecular Clusters: Application and Limitations of the Weak Interaction Model to the (C$_{6}$H$_{6}$)$_{13}$B$_{2u}$ ← A$_{1g}$0$^{0}$ $_{0}$ Spectrum

Electrochemical and Photochemical Conversion of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] into [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$]

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Electrochemical and Photochemical Conversion of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] into [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$]

Content Provider	Springer Nature Link
Author	Vergeer, Frank W. Mahabiersing, Taasje Loza Diz, Enrique Süss Fink, Georg Hartl, František
Copyright Year	2004
Abstract	Electrochemical and photochemical properties of the tetrahedral cluster [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] were studied in order to prove whether the previously established thermal conversion of this cluster into the hydrogenated derivative [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$] also occurs by means of redox or photochemical activation. Two-electron reduction of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] results in the loss of CO and concomitant formation of the dianion [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{12}$]$^{2−}$. The latter reduction product is stable in CH$_{2}$Cl$_{2}$ at low temperatures but becomes partly protonated above 283 K into the anion [Ru$_{3}$Ir(μ-H)$_{2}$(CO)$_{12}$]$^{−}$ by traces of water. The dianion [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{12}$]$^{2−}$ is also the product of the electrochemical reduction of [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$] accompanied by the loss of H$_{2}$. Stepwise deprotonation of [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$] with Et$_{4}$NOH yields [Ru$_{3}$Ir(μ-H)$_{2}$(CO)$_{12}$]$^{−}$ and [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{12}$]$^{2−}$. Reverse protonation of the anionic clusters can be achieved, e.g., with trifluoromethylsulfonic acid. Thus, the electrochemical conversion of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] into [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$] is feasible, demanding separate two-electron reduction and protonation steps. Irradiation into the visible absorption band of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] in hexane does not induce any significant photochemical conversion. Irradiation of this cluster in the presence of CO with λ $_{irr}$>340 nm, however, triggers its efficient photofragmentation into reactive unsaturated ruthenium and iridium carbonyl fragments. These fragments are either stabilised by dissolved CO or undergo reclusterification to give homonuclear clusters. Most importantly, in H$_{2}$-saturated hexane, [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] converts selectively into the [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$] photoproduct. This conversion is particularly efficient at λ $_{ irr }$>340 nm.
Starting Page	47
Ending Page	59
Page Count	13
File Format	PDF
ISSN	10407278
Journal	Journal of Cluster Science
Volume Number	15
Issue Number	1
e-ISSN	15728862
Language	English
Publisher	Kluwer Academic Publishers-Plenum Publishers
Publisher Date	2004-01-01
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry Physical Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry Biochemistry Condensed Matter Physics Materials Science

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Reinvestigation of the reaction of [Ru$_{3}$(CO)$_{12}$] with 2-mercaptobenzothiazole: X-ray structure of [(μ-H)$_{2}$Ru$_{3}$ (μ-η$^{2}$-C$_{7}$H$_{4}$NS$_{2}$)(μ$_{3}$-η$^{2}$-C$_{7}$H$_{4}$NS$_{2}$)(CO)$_{7}$]

The Thermolysis of [Ru$_{3}$(CO)$_{12}$] in Cyclohexene: Synthesis and Charaterisation of the New Clusters [Ru$_{3}$H$_{2}$(CO)$_{9}$(μ$_{3}$-η$^{1}$:η$^{2}$:η$^{1}$-C$_{6}$H$_{8}$)] and [Ru$_{5}$(CO)$_{12}$(μ$_{4}$-η$^{2}$-C$_{6}$H$_{8}$)(η$^{4}$-C$_{6}$H$_{8}$)]

Reactions of Ru$_{3}$(CO)$_{12}$ with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru$_{3}$(CO)$_{9}$[μ$_{3}$-η$^{2}$-HC=N(CH$_{2}$)$_{3}$Si(OEt)$_{3}$]

Bridging and chelating diphosphine ligands in Ru$_{3}$(μ-H)(μ-N=CPh$_{2}$)(CO)$_{8}$(P—P). X-ray diffraction structures of Ru$_{3}$(μ-H)(μ-N=CPh$_{2}$)(CO)$_{8}$(dmpe) and Ru$_{3}$(μ-H)(μ-N=CPh$_{2}$)(CO)$_{8}$(bpcd)

Regiospecific CO substitution in (μ-H)Ru$_{3}$(μ$_{3}$− η$^{3}$-CHCHCMe)(CO)$_{9}$ by 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione(bpcd). X-ray structure of (μ-H)Ru$_{3}$(μ$_{3}$−η$^{3}$-CHCHCMe)(CO)$_{7}$(bpcd)⋅MeOH

Reactions of Triruthenium Clusters with Quinolines: X-Ray Structures of [Ru$_{3}$(μ-CO)(CO)$_{7}${μ$_{3}$-η$^{2}$-P(C$_{6}$H$_{5}$)CH$_{2}$P(C$_{6}$H$_{5}$)$_{2}$)}{μ-η$^{2}$-C$_{9}$H$_{5}$(CH$_{3}$)N}] and [Ru$_{3}$(CO)$_{10}$(μ-H){μ-η$^{2}$-C$_{9}$H$_{6}$N}]

Homogeneous catalytic hydrogenation of diethyl and diphenylacetylene and isomerization ofcis-stilbene in the prescence of [(C$_{5}$H$_{5}$)Ru$_{3}$(μ-CO)(μ $_{3}$-CO)(C$_{2}$Ph$_{2}$)]

Synthesis and characterization of the [Ru(η$^{5}$-C$_{5}$Me$_{4}$CF$_{3}$)(CO)$_{2}$]$_{2}$ and Ru$_{6}$(μ$_{3}$-H)(η$_{2}$-μ$_{4}$-CO)$_{2}$(μ-CO)(CO)$_{12}$(η$^{5}$-C$_{5}$Me$_{4}$CF$_{3}$) complexes

Electrochemical and Photochemical Conversion of [Ru$_{3}$Ir(μ $_{3}$-H)(CO)$_{13}$] into [Ru$_{3}$Ir(μ-H)$_{3}$(CO)$_{12}$]

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