Metallophilicity in Annular Ru2M2 Derivatives of (HMB)RuII(tpdt) versus (Bis)-η2-dithiolate Bonding in Ru2M Derivatives of Cp*RuIII(tpdt) (HMB = η6-C6Me6; Cp* = η5-C5Me5; M = CuI, AgI,II, AuI; tpdt = 3-thiapentane-1,5-dithiolate)

The reaction of [(HMB)RuII(η3-tpdt)] (1:  HMB = η6-C6Me6; tpdt = S(CH2CH2S-)2) with [Cu(MeCN)4]PF6, AgPF6, and (PPh3)AuCl gave the annular species [{(HMB)RuII(μ3-η1:η1:η3-tpdt)}2(M)2]2+ [3:  M = CuI; 3A:  (M)2 = CuI, CuI(MeCN); 4:  M = AgI ; 6:  M = AuI], isolated as PF6 salts in high yields. Complex 6 was formed in a reversible process with [{(HMB)RuII(μ-η1:η3-tpdt)}(AuPPh3)]+ (5) involving dissociation/association of PPh3. Similar reactions of [Cp*RuIII(η3-tpdt)] (2:  Cp* = η5-C5Me5) gave, respectively, the cationic metal−metal bonded Ru2M complexes [{Cp*Ru(μ-η2:η3-tpdt)}2M]n+ (7:  M = CuI, n = 1; 8: M = AgII, n = 2) and [{Cp*Ru(μ-η1:η3-tpdt)}(AuPPh3)]+ (9), isolated as PF6 salts in 71, 73, and 72% yields, respectively. In MeCN or THF for an extended period, 9 underwent transformation to a mixture of complexes, from which [{Cp*Ru}2{μ-η6-(S(CH2)2S(CH2)2SAuPPh3)2}]2+ (10), containing a μ-S2 bridge, and [{Cp*Ru(μ3-η1: η1:η3-tpdt)}(AuPPh3)2]+ (11) could be identified. The new complexes, 3−9 and 11, were all...