Multimetallic Complexes and Functionalized Nanoparticles Based on Oxygen- and Nitrogen-Donor Combinations

The versatile precursors [Ru(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)(2)] (BTD = 2,1,3-benzothiadiazole) and [Ru(C(C CPh) CHPh)Cl(CO)(PPh3)(2)] were treated with isonicotinic acid, 4-cyanobenzoic acid, and 4-(4-pyridyl)benzoic acid under basic conditions to yield [Ru(vinyl)(O2CC5H4N)(CO)(PPh3)(2)], [Ru(vinyl)(O2CC6H4CN-4)(CO)(PPh3)(2)], and [Ru(vinyl){O2CC6H4(C5H4N)-4}(CO)(PPh3)(2)], respectively. The osmium analogue [Os(CH=CHC6H4Me-4)(O2CC5H4N)-(CO)(PPh3)(2)] was also prepared. cis-[RuCl2(dppm)(2)] was used to prepare the cationic compounds [Ru(O2CC5H4N)(dppm)(2)](+) and [Ru{O2CC6H4(C5H4N)-4}(dppm)(2)](+). The treatment of 2 equiv of [Ru(C(CCPh)=CHPh)(O2CC5H4N)(CO)(PPh3)(2)] and [Ru(O2CC5H4N)(dPPm)(2)](+) with AgOTf led to the trimetallic compounds [{Ru(C(C CPh)==CHPh)(CO)-(PPh3)(2)(O2CC5H4N))(2)Ag](+) and [{Ru(dPPm)(2)(O2CC5HN)}(2)Ag](+). In a similar manner, the reaction of [Ru(O2CC3H4N)(dppm)](+) with PdCl2 or K2PtCl4 yielded [{Ro(dPPm)(2)(O2CC5H4N)}(2)MCl2](2+) (M = Pd, Pt). The reaction of [RuHCl(CO)(BTD)(PPh3)(2)] with HC CC6H4F-4 provided [Ru(CH=CHC6H4F-4) Cl(CO)(BTD)(PPh3)(2)], which was treated with isonicotinic acid and base to yield [Ru(CH=CHC6H4F-4)(O2CC5H4N)(CO)(PPh3)(2)]. The addition of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) resulted in the formation of [Ru(CH=CHC6H4F-4){O2CC5H4N(AuC6F5)}-(CO)(PPh3)(2)]. Similarly, [Ru(vinyl)(O2CC6H4CN-4)(CO)(PPh3)(2)] reacted with [Au(C6F5)(tht)] to provide [Ru(vinyl){O2CC6H4(CNALIC(6)F(5))-4}(C)(PPh3)zi. The reaction of 4-cyanobenzoic acid with [Au(C6F5)(tht)] yielded [Au(C6F5)(NCC6H4CO2(PPh3)(2)]. This compound was used to prepare [Ru(CH=CHC6H4F-4){O2CC6H4(CNAuC6F5)-4}(CO) (PPh3)(2)], which was also formed on treatment of (Ru(CH=CHC6H4F-4)(O2CC6H4CN-4)(CO)(PPh3)2] with [Au(C(6)F5)(tht)]. The known compound [RhCl2(NC5H4CO2)(NC5H4CO2Na)(3)] and the new complex [RhCl2{NC5H4(C6H4CO2)-4}{NC5H4(C6H4CO2Na)-4}(3)] were prepared from RhCl3 center dot 3H(2)O and isonicotinic acid or 4-(4-pyridyl)benzoic acid, respectively. The former was treated with [Ru(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)(2)] to yield [RhCl2{NC5H4CO2(Ru(CH=CHC6H4Me-4)(CO)(PPh3)(2))(4)]Cl. As an alternative route to pentametallic compounds, the Pd-coordinated porphyrin [(PdTPP)(p-CO2H)(4)] was treated with 4 equiv of [Ru(CH=CHR)CI(CO)(BTD)(PPh3)(2)] in the presence of a base to yield [(PdTPP)(p-CO2Ru(CH=CHR)(CO)(PPh3)(2)](4)] (R = C6H4Me-4, CPh2OH). Where R = CPh2OH, treatment with HBF4 led to the formation of [(Pd-TPP){p-CO2Ru(=CHCH=CPh2)(CO)(PPh3)(2)}(4)](BF4)(4)center dot[(Pd-TPP){p-CO2Ru(dppm)(2)}(4)](PF6)(4) was prepared from [(Pd-TPP)(P-CO2H)(4)] and cis-[RuCl2(dPPm)(2)]. The reaction of AgNO3 with sodium borohydride in the presence of [Ru(O2CC5H4N)(dPPm)(2)](+) or [RuR{O2CC6H4(C5H4N)-4}(dppm)(2)](+) provided silver nanoparticles Ag@[NC5H4CO2Ru(dppm)(2)](+) and Ag@[NC5H4{C6H4CO2Ru(dppm)(2)}-4](+).