Ruthenium ligand substitution reactions

The possibility of the practical application of the catalytic photode-composition of water based on the reactivity of the excited states of tris(2,2 -bipyridine) complexes of ruthenium(III) and ruthenium(II) has attracted considerable interest, but it is now clear that the efficiency of this process is limited not only by the lack of efficient catalysts, particularly for the dioxygen-evolving path, but also by both thermal and photochemical ligand oxidation 1,2) and ligand substitution reactions (3) of the 2,2 -bipyridine complexes. The stoichiometrically analogous tris(2,2 -bipyridine) and tris(l,10-phenanthroline) complexes of both... 

From a practical standpoint, it is of interest to devise a one-step synthesis of the catalyst. Since both reactions 2 and 3 are ligand substitution reactions, it is quite conceivable that both steps can be carried out at the same time. When we reacted [Ru(COD)Cl2]n with BINAP and sodium acetate in acetic acid, we indeed obtained Ru(BINAP)(OAc)2 in good yields (70-80%). Interestingly, when the reaction was carried out in the absence of sodium acetate, no Ru(BINAP)(OAe)2 was obtained. The product was a mixture of chloro-ruthenium-BINAP complexes. A 3ip NMR study revealed that the mixture contained a major species (3) (31P [ H] (CDCI3) Pi=70.9 ppm P2=58.3 ppm J = 52.5 Hz) which accounted for more than 50% of the ruthenium-phosphine complexes (Figure 2). These complexes appeared to be different from previously characterized and published Ru(BINAP) species (12,13). More interestingly, these mixed complexes were found to catalyze the asymmetric hydrogenation of 2-(6 -methoxy-2 -naphthyl)acrylic acid with excellent rates and enantioselectivities. 

Water-soluble derivatives of alkylidenes 8 and 9 were prepared via phosphine ligand substitution reactions. Exchange of the phosphines in 8a for PhP(p-C6H4S03-Na)2 afforded a water-soluble vinyl alkylidene [20]. This alkylidene was soluble in water, but the triarylphosphine ligands were too small and insufficiently electron-donating to produce an active catalyst [48], Analogous substitution of the phosphines in 9 a for more sterically demanding, electron-rich, water-soluble phosphines yielded ruthenium alkylidenes 10 and 11 (Scheme 2), which were soluble in both water and methanol [49]. 

The pentammine aqua ion [Ru(NH3)j(H20)]2+, best made by zinc amalgam reduction and aquation of [Ru(NH3)5C1]2+, undergoes extensively studied substitution reactions first order in both the ruthenium complex and the incoming ligand (e.g. NH3, py) and is a convenient source of other... 

Scheme 3 shows the details of the synthetic strategy adopted for the preparation of heteroleptic cis- and trans-complexes. Reaction of dichloro(p-cymene)ruthenium(II) dimer in ethanol solution at reflux temperature with 4,4,-dicarboxy-2.2 -bipyridine (L) resulted the pure mononuclear complex [Ru(cymene)ClL]Cl. In this step, the coordination of substituted bipyridine ligand to the ruthenium center takes place with cleavage of the doubly chloride-bridged structure of the dimeric starting material. The presence of three pyridine proton environments in the NMR spectrum is consistent with the symmetry seen in the solid-state crystal structure (Figure 24). 

The chemistry of these compounds has not been investigated in detail. Scheme 12 summarizes some of the chemistry that has been established for the ruthenium complex RugClCO) (192). In general, the octahedral metal-carbido skeleton is maintained, substitution reactions occurring with phosphine, phosphites, and arsine ligands. Base attack leads to the production of the anion [Ru8C(CO)16P, which is... 

Hetero site reactivity The simplest difference between a cluster and a mononuclear complex is that the cluster can do two or more things where a mononuclear complex can do one. Simple as it is, this difference has hardly ever been verified other than in multiple ligand substitutions. One verification is hetero site reactivity, i.e., different modes of reaction at different sites on one and the same cluster. Two examples of this appear to exist. Different phosphine ligands substitute CO on different metal atoms in H2FeRu3(CO),3 depending on their size and basicity (210), and Ru2Co2 (CO), 3 reacts with H2 at the ruthenium atoms (cf. Section IV, A) and... 

Operating within the framework of the Chauvin mechanism, the main consideration for the reaction mechanism is the order of events in terms of addition, loss and substitution of ligands around the ruthenium alkylidene centre. Additionally, there is a need for two pathways (see above), both being first order in diene, one with a first-order dependence on [Ru] and the other (which is inhibited by added Cy3P) with a half-order dependence on [Ru]. From the analysis of the reaction kinetics and the empirical rate equation thus derived, the sequence of elementary steps via two pathways was proposed, one non-dissociative (I) and the other dissociative (II), as shown in Scheme 12.20. The mechanism-derived rate equation is also shown in the scheme and it can thus be seen how the constants A and B relate to elementary forward rate constants and equilibria in the proposed mechanism. 

With respect to the derivatives of metal carbonyls, the substituted metal carbonyls of the VIB Group (e.g., Mo(CO)apya), the halogenocar-bonyls of iron, ruthenium, iridium, and platinum, the hydridocarbonyls H2Fe(CO)4 and HCo(CO)4 discovered in 1931 and 1934, and the nitrosyl carbonyls FelCOj NOjg and Co(CO)3NO were the most important (/). The known anionic CO complexes were limited to [HFe(CO)J and [Co(CO)J-. For studies of substitution reactions of metal carbonyls at this time, work was almost totally limited to reactions involving the classical N ligands such as NH3, en, py, bipy, and phen. 

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