A series of triisopropylstibine ruthenium and osmium complexes including the X-ray crystal structure of [RuCl 2(CO)(Sb iPr 3) 3] and [RuCl 2(CCCPh 2)(CO)(Sb iPr 3) 2

Abstract

With [( p-cym)RuCl 2] 2 ( 1) as the starting material, the halfsandwich-type complexes [( p-cym)RuCl 2(Sb iPr 3)] ( 2) and [( p-cym)RuCl(Sb iPr 3) 2]PF 6 ( 3) were prepared. Treatment of RuCl 3·3H 2O in ethanol gave, after addition of Sb iPr 3, the monocarbonyl compound [RuCl 2(CO)(Sb iPr 3) 3] ( 4), which reacted with CO by ligand exchange to yield [RuCl 2(CO) 2(Sb iPr 3) 2] ( 5). The reaction of RuCl 3·3H 2O in ethanol, in the presence of Na 2CO 3, afforded the chloro(hydrido) derivative [RuHCl(CO)(Sb iPr 3) 3] ( 6). Analogously, using OsCl 3·3H 2O as the starting material, the chloro(hydrido)osmium complex [OsHCl(CO)(Sb iPr 3) 3] ( 8) was prepared. The reactions of 8 with C 2H 4, C 2(CO 2Me) 2 and NaBH 4 led to the formation of compounds 9, 10 and 11, which all contain the Os(Sb iPr 3) 2 unit as a building block. While treatment of 6 with C 2(CO 2Me) 2 yielded the substitution product [RuHCl(CO)(MeO 2CCCCO 2Me)(Sb iPr 3) 2] ( 14), the corresponding reaction of 6 with HCCPh and HCCCPh 2OH afforded the alkynyl and allenylidene ruthenium(II) complexes [RuCl(CCPh)(CO)(Sb iPr 3) 3] ( 16) and [RuCl 2(CCCPh 2)(CO)(Sb iPr 3) 2] ( 17), respectively. Compounds 4 and 17 were characterized by X-ray crystal structure analysis.