Use of the Cationic Fragments [Ru(?5-C5H5) (MeCN)3]+ and [M(?6-C6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as Ionic Coupling Reagents in the Synthesis of the Clusters [Os4M2(CO)12(?6-C6H5R)], [Os4M(CO)12(?6-C6H6)(Au2dppm)] and [Os5Ru(CO)15(?5-C5H5)(AuPPh3)]*

Autor: Al-Mandhary, Muna R. A., Buntem, Radchada, Doherty, Cheryl L., Edwards, Andrew J., Gallagher, John F., Lewis, Jack, Li, Chi-Keung, Raithby, Paul R., Ramirez de Arellano, M. Carmen, Shields, Gregory P.
Zdroj: Journal of Cluster Science; June 2005, Vol. 16 Issue: 2 p127-150, 24p
Abstrakt: Abstract The clusters [H2Os4M(CO)12eta6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12eta6-C6H6)]2- which react with [M'eta6-C6H5R) (MeCN)3]2+(M'=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM'eta6-C6H5R)2]. Whereas [Os4(CO)12M2eta6-C6H6)2] (M=Os, Ru) have one Meta6-C6H6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO)12OsRueta6-C6H6)2] has the Rueta6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12eta6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO)15] with K/Ph2CO and coupling with [Rueta5-C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Rueta5-C5H5)]- which reacts with [AuPPh3]+ generating [Os5(CO)15Rueta5-C5H5)(AuPPh3)] with the “Ru(C5H5)” unit in the terminal {3} site.
Databáze: Supplemental Index