Multimetallic Arrays: Symmetrical and Unsymmetrical Bi-, Tri-, and Tetrametallic Organometallic Complexes of Ruthenium(II) and Osmium(II)

The cationic complex [Ru(C(C CPh) CHPh)(S,CNC4HgNH2)(CO)(PPh3)(2)](+) was prepared from the reaction of [Ru(C(C CPh)=CHPh)Cl(CO)(BTD)(PPh3)(2)] (BTD = 2,1,3-benzothiadiazole) with the zwitterionic dithiocarbamate H,NCANCS, and characterized structurally. In situ generation of the metal lad ithiocarbamate [Ru(C(C CPh)=CHPh)(SCNC4H8NCS2)(CO)(PPh3)(2)] followed by treatment with [Ru(C(C CPh)=CHPh)c](CO)(BTD)(PPh3)(2)] yielded the symmetrical bimetallic complex [{Ru(C(C CPh)=CHPh)(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2)]. The same product was also accessible by reaction of KS2CNC4H8NCS2K with [Ru(C(C CPh)=CHPh)C](CO)(BTD)(PPh3)(2)]. This direct method also yielded the symmetrical bimetallic complexes [[Ru(CH=CHR)(CO)(PPh3)(2)](2)(S2CNC4H8NCS2)] (R = Bu-t, CPh,OH, C6H4Me-4, CO2Me, CH2OSiMe2,Bu-t) and a tetrametallic species when R = C5H4FeC5H5. The osmium analogues [{Os(CR1=CHR2)(CO)(PPh3)(2))(2)(S2CNC4H8NCS2)] (R1 = C CPh, R-2 = Ph; R-1 = H, R-2 = C6H4Me-4) were also prepared by this method. The stepwise deprotonation and functionalization of [Ru(C(C CPh)=CHPh)(S2CNC4H8NH2)(CO)(PPh3)(2)](+) with NEt3 and CS, was utilized in the generation of the unsymmetrical complexes [{Ru(C(C=-CPh)=CHPh)(CO)(PPh3)(2)} (S(2)CNC(4)HsNCS,) fRu(CH=CHR)(CO)(PPh3)2)] (R = Bu-t, CPh2,OH, C6H4Me-4, COMe, CH2OSiMe2But, C5H4FeC5H5) and the heterobimetallic variant [[Ru(C(C cPh) =(CHPh)(CO)(PPh3)(2))(S2CNC4HNCS2){Os(CH=CHC6H4Me-4)(CO)(PPh3)(2)}]. The mixed carbonyl-thiocarbonyl complex [IRu(C(C CPh)=CHPh)(CO)(PPh3)(2))(S2CNC4H8NCS2)IRu(C(C CPh)=CHPh)(CS)(PPh3)(2))] was also prepared by the same stepwise procedure. These are the first reported examples of alkenyl species bridged by a dithiocarbamate ligand. The similarly unprecedented linked bis(alkynyl)diruthenium complex [(Ru(C CBut)(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2)] was prepared by heating [{Ru(CH=CHC6H4Me-4)(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2)] with excess HC CBut. The first molecular complex bearing all three group 8 metals, [{Ru(C(C CPh)=CHPh)-(CO)(PPh3)(2)}(2)(S2CNC4H8NCS2){Os(CH=CHFc)(CO)(PPh3)(2))], was achieved through the reaction of [Ru(C(C=-CPh)=CHPh)(S2CNC4H2NH2)(CO)(PPh3)(2)](+) with [s(CH=CHFc)CI(CO)(BTD)(PPh3)(2)] (Fc = C5H4FeC5H5, BTD = 2,1,3-benzothiadiazole). Further trimetallic species [(Ru(C(C CPh)=CHPh)(CO)(PPh3)(2)(S2CNC4H8NCS,))(2)M] (M = Ni, Pd, Pt, Zn) were prepared by the reaction of [Ru(C(C CPh)=CHPh)(S2CNC4H2)(CO)(PPh3)(2)](+) with Ni(OAC)(2),PdCl2(NCMe)(2),PtCl2(NCPh)(2) and Zn(OAC)(2) in the presence of NEt3 and CS2.