Metallacarbonares containing exo-thio and exo-phosphinocarbonare ligands. Tehir application in catalysis Authors Clara Viñas i Teixidor Francesc Teixidor i Bombardó Rosario Núñez Aguilera Abstract Metallacarboranes containing exo-thioether or exo-phosphinocarboranes were synthesized and characterized. These complexes were obtained from the reaction of tetramethylammonium or cesium salt of the nido ligand with Rh(I), Pd(II) or Ru(II) complexes incorporating ancillary ligands. Although two molecular structures were possible, the closo and the exo-nido, generally only the exo-nido tautomer was formed. The cluster was coordinated with the metal through the S or P atom and one or two B-HM interactions, depending on the metal. These exo-nido rhoda and ruthenacarboranes catalyzed the hydrogenation of terminal alkenes in very good yield but were not active in the hydrogenation of internal alkenes. Ruthenamonophosphinocarboranes were also active in the hydrogenation of the 1-hexene, with a higher selectivity than the respective rhodacarboranes. On the other hand, while [Rh(7-PPh2-8-R-7,8- C2B9H10)(PPh3)2] (R= H, Me) catalyzed the hydrogenation of methacycline to doxycycline with high yield (ca. 100%) and very high diastereoselectivity (> 99%), ruthenacarboranes were not active. The closo species [closo-3-(C8H13)-1-SR-2- R-3,2,1-RhC2B9H9] (R= Ph; R= Me, Ph) obtained from exonido-[ Rh(7-SR-8-R-7,8-C2B9H10)(cod)] were very efficient catalysts in the hydrogenation of cyclohexene exhibiting higher activity than the parent exo-nido isomers. All these complexes were recoverable after completion of the catalytic reaction. In addition to hydrogenation, exo-nido rhoda and ruthenamonothio and monophosphinocarboranes were also tested as catalyst precursors in the insertion of carbenes into C=C and O-H bonds. Downloads Text complet Published 2002-05-08 Issue 1-4 Section Research reviews License This work is subject, unless the contrary is indicated in the text, the photographs or in other illustrations, to an Attribution —Non-Commercial— No Derivative Works 3.0 Creative Commons License, the full text of which can be consulted at http://creativecommons.org/licenses/by-nc-nd/3.0/. You are free to share, copy, distribute and transmit the work provided that the author is credited and reuse of the material is restricted to non-commercial purposes only and that no derivative works are created from the original material.