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

• Published in: Journal of cluster science Vol. 15; no. 1; pp. 47 - 59
• Main Authors: Vergeer, Frank W., Mahabiersing, Taasje, Lozano Diz, Enrique, Süss-Fink, Georg, Hartl, František
• Format: Journal Article
• Language: English
• Published: New York Springer Nature B.V 01.03.2004
• Subjects: Absorption spectra; Anions; Carbonyls; Chemical reduction; Clusters; Dichloromethane; Fragments; Hexanes; Iridium; Irradiation; Low temperature; Protonation; Ruthenium
• ISSN: 1040-7278; 1572-8862
• DOI: 10.1023/B:JOCL.0000021252.65477.bc

Electrochemical and photochemical properties of the tetrahedral cluster [Ru3Ir(μ3-H)(CO)13] were studied in order to prove whether the previously established thermal conversion of this cluster into the hydrogenated derivative [Ru3Ir(μ-H)3(CO)12] also occurs by means of redox or photochemical activation. Two-electron reduction of [Ru3Ir(μ3-H)(CO)13] results in the loss of CO and concomitant formation of the dianion [Ru3Ir(μ3-H)(CO)12]2−. The latter reduction product is stable in CH2Cl2 at low temperatures but becomes partly protonated above 283 K into the anion [Ru3Ir(μ-H)2(CO)12]− by traces of water. The dianion [Ru3Ir(μ3-H)(CO)12]2− is also the product of the electrochemical reduction of [Ru3Ir(μ-H)3(CO)12] accompanied by the loss of H2. Stepwise deprotonation of [Ru3Ir(μ-H)3(CO)12] with Et4NOH yields [Ru3Ir(μ-H)2(CO)12]− and [Ru3Ir(μ3-H)(CO)12]2−. Reverse protonation of the anionic clusters can be achieved, e.g., with trifluoromethylsulfonic acid. Thus, the electrochemical conversion of [Ru3Ir(μ3-H)(CO)13] into [Ru3Ir(μ-H)3(CO)12] is feasible, demanding separate two-electron reduction and protonation steps. Irradiation into the visible absorption band of [Ru3Ir(μ3-H)(CO)13] in hexane does not induce any significant photochemical conversion. Irradiation of this cluster in the presence of CO with λirr>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 H2-saturated hexane, [Ru3Ir(μ3-H)(CO)13] converts selectively into the [Ru3Ir(μ-H)3(CO)12] photoproduct. This conversion is particularly efficient at λirr>340 nm.