Ru II Complexes with -S and -O Donors

Cix-RuClj(dmso) is made from RuClj and DMSO as yellow crystals [937], from RuClj, and DMSO [938] or from mer-RuCl3((dmso)3Cl3 and (dppe) with DMSO, this last method giving the orange orthorhombic polymorph [939], X-ray crystal structures on the monoclinic and orthorhombic polymorphs (cf. the brief review in ref. [939]) show essentially the same structures (Fig. 1.43). The orthorhombic form has cis chloro ligands, with one O- and three S-bonded (dmso) 

The IR spectra of the normal and deuteriated form have been reported [937]. It is evident that the cis form is the thermodynamically stable one [940] and it is this which is likely to be the initial species in catalytic reactions. 

CIS-[Ru(H20)2(dinso) ] is made from as-RuClj(dmso) and Ag(BF ) in aq. EtOH. The system c/s-[Ru(H20)j(dmso) ] Vaq. Na(ClO) or TBHP/CH Cl oxidised alkanes such as adamantane, cyclo-octane, -heptane and -hexane to the corresponding alcohols and ketones as did [Ru(Hj0) PWjj(0)3g ] . A free-radical mechanism may be involved for the TBHP oxidations, but those with (C10) probably involve oxoruthenate(VI) or oxoruthenate(IV) intermediates [823], The oxidative destruction of a-chlorinated alkenes by CM-[Ru(HjO)2(dmso) ] Vaq. Oxone /Me(CH3) jN(HSO ) MCj to carboxylic acids and ultimately to CO and HCl was reported [946], 

RuCl2(dinso)2(pcbo) (pcbo=iV-phenylcarbamoyl derivative, with H, Me, OMe, Cl or NO as a p-substituent) is made from cw-RuCl Cdmso) and the ligand. As RuCl2(dmso)2(pcbo)/PhlO/water- CHjCN it epoxidised norbomene and cis-cyclo-octene [950], 

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