Control of the photochemistry of Ru-3(CO)(12) and Os-3(CO)(12) by variation of the solvent

Authors
Citation
Ne. Leadbeater, Control of the photochemistry of Ru-3(CO)(12) and Os-3(CO)(12) by variation of the solvent, J ORGMET CH, 573(1-2), 1999, pp. 211-216
Citations number
19
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
JOURNAL OF ORGANOMETALLIC CHEMISTRY
ISSN journal
0022328X → ACNP
Volume
573
Issue
1-2
Year of publication
1999
Pages
211 - 216
Database
ISI
SICI code
0022-328X(19990131)573:1-2<211:COTPOR>2.0.ZU;2-0
Abstract
The synthetic potential of the photosubstitution of CO by two-electron dono r ligands in M-3(CO)(12) [M = Ru, Os] has been investigated. When used as p hotolysis media, diethyl ether, ethyl acetate and acetonitrile act as photo fragmentation quenchers allowing for the synthesis of photosubstitution pro ducts in high yield. UV photolysis of M-3(CO)(12) with added triphenylphosp hine in these photolysis media leads to M-3(CO)(12-n)(PPh3)(n) (n = 1, 2 or 3). Prolonged photolysis with added tricyclohexylphosphine generates the h ighly sterically crowded complex M-3(CO)(9)(PCy3)(3). Photolysis with thiol s, RSH (R = Et, Ph), leads to the thiolato complexes HM3(mu-SR)(CO)(10), pr olonged photolysis of which generates the corresponding sulphido cluster M- 3(mu(3)-S)(CO)(10). Photolysis of M-3(CO)(12) in acetonitrile with no added ligand results in the generation of M-3(CO)(12-n)(MeCN)(n) (n = 1 or 2). T his offers a route to these complexes without the need for the use of oxidi sing agents such as trimethylamine-N-oxide. Photolysis of an ethene-saturat ed diethyl ether or ethyl acetate solution of M-3(CO)(12) leads to no net p hotoreaction in the case of ruthenium, whereas, for osmium, the olefin comp lex Os(CO)(4)(eta(2)-C2H4) is formed. This highlights the difference in the photosubstitution mechanism for Ru-3(CO)(12) and Os-3(CO)(12). (C) 1999 El sevier Science S.A. All rights reserved.