A series of triisopropylstibine ruthenium and osmium complexes including the X-ray crystal structure of [RuCl2(CO)(SbiPr3)3] and [RuCl2(CCCPh2)(CO)(SbiPr3)2]

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