Organoruthenium chalcogen complexes: synthesis of tert-butyl-cyclopentadienyl dicarbonyl ruthenium thio- and seleno-carboxylate complexes and crystal structure determination of (tBuC5H4)Ru(CO)2SCO(3-NO2C6H4) and (tBuC5A4)Ru(CO)2SeCO(3,5-(NO2)2C6H3)

Abstract The substituted cyclopentadienyl organoruthenium dimers [( t BuC 5 H 4 )Ru(CO) 2 ] 2 (I) and [(1,3-Bu 2 -C 5 H 3 )Ru(CO) 2 ] 2 (II) were prepared from the reaction of Ru 3 (CO) 12 with t-butyl cyclopentadiene or 1,3-di-t-butylcyclopentadiene. The thermal reaction of dimer I with elemental sulfur or selenium afforded mixtures of organoruthenium polysulfides and polyselenides from which the binuclear pentasulfur and pentaselenium bridged complexes [( t BuC 5 H 4 )Ru(CO) 2 ] 2 (μ-S 5 )(III) and [( t BuC 5 H 4 )Ru(CO) 2 ] 2 (μ-Se 5 )(IV) were isolated and characterized. The organoruthenium sulfides and selenides readily react with acid chlorides RCOCI to give the S-bonded and the Se-bonded monothio- and monoseleno-carboxylate derivatives ( t BuC 5 H 4 )Ru(CO) 2 ECOR)(E  S, Se; R  3-NO 2 C 6 H 4 , 4-NO 2 C 6 H 4 , 3,5-(NO 2 ) 2 C 6 H 3 ). The crystal structures of [( t BuC 5 H 4 )Ru(CO) 2 SCO(3-NO 2 C 6 H 4 )] and [( t BuC 5 H 4 )Ru(CO) 2 SeCO(3,5-(NO 2 ) 2 C 6 H 3 )] were determined.