Organoruthenium chalcogen complexes: synthesis of tert-butyl-cyclopentadienyl dicarbonyl ruthenium thioand seleno-carboxylate complexes and crystal structure determination of ( tB~-C5H4) Rut CO) ,SCd 3-NO,-C,H,) and ( tB~-C5H4) Rut CO) ,SeCd 3,5-t NO,) &,H,)

The substituted cyclopentadienyl organoruthenium dimers [(?Bu-C,H,)Ru(CO),l,(I) and [(1,3-?Bu,-C,H,)Ru(CO),],(II) were prepared from the reaction of RUG,, 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 [(?Bu-C,H,)Ru(CO),],( @,)(III) and [(?Bu-C,H,)Ru(CO),],( p-Se&IV) were isolated and characterized. The organoruthenium sulfides and selenides readily react with acid chlorides RCOCl to give the S-bonded and the Se-bonded monothio- and monoseleno-carboxylate derivatives (?Bu-C~H,)RU(CO)~ECORXE = S, Se; R = 3-NO,-C6H,, CNO,-C,H,, 3,5-(N0,)2-C6H3). The crystal structures of [(?Bu-C5H,)Ru(CO),SC0(3-NO,-C,H,)] and [(?Bu-C,H,)Ru(CO),SeC0(3,5-(NO,),- C,H,)] were determined.