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)(S2CNC4H8NH2)(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 H2NC4H8NCS2 and characterized structurally. In situ generation of the metalladithiocarbamate [Ru(C(CCPh)CHPh)(S2CNC4H8NCS2)(CO)(PPh3)2] followed by treatment with [Ru(C(CCPh)CHPh)Cl(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)Cl(CO)(BTD)(PPh3)2]. This direct method also yielded the symmetrical bimetallic complexes [{Ru(CHCHR)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (R = But, CPh2OH, C6H4Me-4, CO2Me, CH2OSiMe2But) and a tetrametallic species when R = C5H4FeC5H5. The osmium analogues [{Os(CR1CHR2)(CO)(PPh3)2}2(S2CNC4H8NCS2)] (R1 = CCPh, R2 = Ph; R1 = H, R2 = 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 CS2 was utilized in the generation of the unsymmetrical complexes [{Ru(C(CCPh)CHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru(CHCHR)(CO)(PPh3)2}] (R = But, CPh2OH, C6H4Me-4, CO2Me, CH2OSiMe2But, C5H4FeC5H5) and the heterobimetallic variant [{Ru(C(CCPh)CHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Os(CHCHC6H4Me-4)(CO)(PPh3)2}]. The mixed carbonyl−thiocarbonyl complex [{Ru(C(CCPh)CHPh)(CO)(PPh3)2}(S2CNC4H8NCS2){Ru(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}(S2CNC4H8NCS2){Os(CHCHFc)(CO)(PPh3)2}], was achieved through the reaction of [Ru(C(CCPh)CHPh)(S2CNC4H8NH2)(CO)(PPh3)2]+ with [Os(CHCHFc)Cl(CO)(BTD)(PPh3)2] (Fc = C5H4FeC5H5, BTD = 2,1,3-benzothiadiazole). Further trimetallic species [{Ru(C(CCPh)CHPh)(CO)(PPh3)2(S2CNC4H8NCS2)}2M] (M = Ni, Pd, Pt, Zn) were prepared by the reaction of [Ru(C(CCPh)CHPh)(S2CNC4H8NH2)(CO)(PPh3)2]+ with Ni(OAc)2, PdCl2(NCMe)2, PtCl2(NCPh)2, and Zn(OAc)2 in the presence of NEt3 and CS2.