Ruthenium(II) dihalogeno-complexes with (C 6H 5) 2P(CH 2) 2SR ligands (RCH 3, C 2H 5, and cyclo-C 6H 11) and their reactions with carbon monoxide and acetonitrile. The crystal structure of trans,cis,cis1-[RuCl 2{(C 6H 5) 2P(CH 2) 2S( cyclo-C 6H 11)- P,S} 2

Abstract

The reaction between cis-[RuCl 2(dmso) 4] (dmso=dimethylsulfoxide) and the phosphine-thioether ligands Ph 2P(CH 2) 2SR (PSR- P,S=Me PSMe, R=Et PSEt, or R= cyclo-C 6H 11 PSCy) affords the ruthenium(II) six-coordinate derivatives [RuCl 2(PSR- P,S) 2]. All complexes have been characterised by means of UV-Vis, IR and 1H, 13C and 31P NMR spectroscopy. Three of the five possible isomers ( cis,cis,cis, cis,cis,trans and trans,cis,cis) of the octahedral complexes have been obtained. The crystal structure of trans,cis,cis-[RuCl 2(PSCy- P,S) 2] has been determined by single-crystal X-ray diffraction analysis. Also cis,cis,trans-[RuI 2(PSR- P,S) 2] derivatives have been prepared from the corresponding dichloro-compounds by halide metathesis. The reaction of [RuCl 2(PSR- P,S) 2] with carbon monoxide gives cationic [RuCl(CO)(PSR- P,S) 2] + or neutral [RuCl 2(CO)(PSCy- P)(PSCy- P,S)] derivatives via RuCl or RuS bond cleavage, respectively. In the case of the diiodo-derivatives the corresponding monocarbonyls [RuI(CO)(PSR- P,S) 2] + are obtained. The reaction of ciskcis,cis- and cis,cis,trans-(RuCl 2(PSMe- P,S) 2] isomers with acetonitrile has also been investigated, and both cis,cis- and cis,trans-[Ru(MeCN) 2(PSMe- P,S) 2] 2+ have been obtained. Both diacetonitrile compounds slowly react with CO yielding the corresponding [Ru(CO)(MeCN)(PSMe- P,S) 2] 2+ derivatives with retention of configuration. Properties, structural features, and reactivity of [RuX 2(PSR- P,S) 2] compounds are compared with that of the ruthenium(II) analogues with phosphine-ether ligands.