Journal of the Chemical Society, Dalton Transactions p. 4171 - 4181 (1996)
Update date:2022-08-05
Topics:
Edwards, Karen J.
Field, John S.
Haines, Raymond J.
Homann, Beverley D.
Stewart, Mark W.
Sundermeyer, Jorg
Woollam, Stephen F.
Protonation of the co-ordinatively unsaturated species [Ru2(μsb-CO)2(CO) 2(μ-etipdp)2] [sb = semi-bridging, etipdp = (PriO)2PNEtP(OPri)2] by acids of non-co-ordinating conjugate bases, e.g. HBF4·OEt2, produced [Ru2(μ-H)(μ-CO)(CO)3(μ-etipdp)2] + which, as established X-ray crystallographically for the PF6- salt, contains both a bridging carbonyl and a bridging hydride ligand. This cationic species is very susceptible to attack by both neutral and anionic nucleophiles affording a range of product types. For instance, its reactions with anions X- which are capable of functioning as monodentate bridging ligands and which preferentially adopt the closed bridging co-ordination mode, e.g. halide and hydrogensulfide ions, afforded products of the type [Ru2(μ-X)H(μsb-CO)(CO)2(μ-etipdp) 2] (X = Cl, Br, I, SH, etc.), resulting from the substitution of a carbonyl group by the nucleophile. On the other hand, anionic nucleophiles such as H- and CN- gave addition products of the type [Ru2HX(CO)4(μ-etipdp)2] (X = H, CN, etc.) in which the hydride and the X- ligand occupy equatorial sites trans disposed with respect to each other, as established in a separate study for [Ru2H2(CO)4(μ-etipdp)2]. Carbon monoxide also afforded a simple addition product, viz. [Ru2H(CO)5(μ-etipdp)2]+, but the majority of the other neutral nucleophiles studied, particularly the unsaturated systems, yielded products resulting from formal insertion of the nucleophile into the Ru-H bond. Thus sulfur produced [Ru2(μ-SH)(CO)4(μ-etipdp)2]+, while unsaturated nucleophiles of general formula X′≡Y′, e.g. PhC≡N and RC≡CH (R = H, Ph, etc.), gave products of the type [Ru2(μ-X′Y′(H)}(CO)4(μ-etipdp) 2]+, e.g. [Ru2{μ-NC(H)Ph}(CO)4(μ-etipdp)2] + or of the type [Ru2{μ-η2-X′Y′(H)}(CO) 4(μ-etipdp)2]+, e.g. [Ru2(μ-η1:η2-CHCHR)(CO) 4(μ-etipdp)2]+. Heterocumulenes X″=Y″=Z″ such as CS2 and PhNCS behaved similarly affording products of general formula [Ru2{μ-η2-X″Y″(H)Z″}(CO) 4(μ-etipdp)2]+ containing five-membered RuX″Y″Z″Ru rings. The co-ordinatively saturated pentacarbonyl [Ru2H(CO)5(μ-etipdp)2]PF6 gave products similar to those afforded by [Ru2(μ-H)(μ-CO)(CO)3(μ-etipdp) 2]PF6 on reaction with systems of the type X'=Y' and X″=Y″=Z″ except that, for terminal alkynes such as PhC≡CH, alkenylcarbonyl-bridged products, e.g. [Ru2{μ-η2-OC(CH=CHPh)}(CO) 4(μ-etipdp)2]PF6, are produced. The crystal structures of the following compounds were determined: [Ru2(μ-H)(μ-CO)(CO)3(μ-etipdp) 2]PF6, [Ru2(μ-I)H(μsb-CO)(CO)2(μ-etipdp) 2], [Ru2{μ-N(CHPh)}(CO)4(μ-etipdp)2]PF 6, [Ru2(μ-η1:η2-CHCH 2)(CO)4(μ-etipdp)2]PF6, [Ru2{μ-η2-OC(CHCHPh)}(CO) 4(μ-etipdp)2]PF6 and [Ru2{μ-η2-SC(H)NPh}(CO) 4(μ-etipdp)2]PF6.
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