Inert metal complexes

In volume 7 reactions of metallic salts, complexes and organometallic compounds are covered. Isomerisation and group transfer reactions of inert metal complexes and certain organometallics (not involving a change in oxidation state) are considered first, followed by oxidation-reduction processes (a) between different valency states of the same metallic element (b) between salts of different... 

Bipyridines were efficiently used in supramolecular chemistry [104], Since the molecule is symmetric no directed coupling procedure is possible. In addition, 2,2 6/,2//-terpyridine ligands can lead to several metal complexes, usually bis-complexes having octahedral coordination geometries [105,106], Lifetimes of the metal-polymeric ligand depend to a great extent on the metal ion used. Highly labile complexes as well as inert metal complexes have been reported. The latter case is very important since the complexes can be treated as conventional polymers, while the supramolecular interaction remains present as a dormant switch. 

Inert metal complexes, 34 145-147 acid-catalyzed paths, 34 167 alteration of leaving group displacement rate, 34 150... 

Octene complexes with gold, 12 348 0-donor, inert metal complexes, 34 156, 158 OH... 

Polynuclear complexes, 32 56 osmium, electrochemistry, 37 321-323 X-ray diffraction, 39 217-225 Polynuclear compounds, inert metal complexes, 34 186... 

The hydrolysis of 1-acetylimidazole202 in the presence of the exchange-inert metal complexes [Co(NH3)5OH]2+, [Cr(OH2)5OH]2+ and [Cr(NH3)5OH]2+ is also of interest. The processes appear to be predominantly nucleophilic in character, as shown by the isolation of a 93% yield of [Co(NH3)5(OCOMe)]2+ in the reaction of [Co(NH3)5OH]2+ with the amide. There is little or no contribution from general base catalysis and this appears to be a feature of MOHn+ reactions of this type. 

A number of reactions of inert metal complexes are nicely explained by a preliminary deprotonation of the NFI2 ligand. These include base hydrolysis (equation 7), NFI — ND exchange,s-NFI racemization, and some N-C bond formation reactions (equation 12). In every case, the rate of the reaction is proportional to the OH concentration and, as mentioned earlier (see Section 1), in favorable cases the deprotonated species can be isolated and characterized. 

Conjugation with Substitution-inert Metal Complexes... 

The kinetics of oxidation of dithiocarbamate anions to thiuram disulfides in 30% aqueous acetone by [Mo(CN)g] , [W(CN)g] , and 10 other substitution-inert metal complexes have also been investigated 61). Dithiocarbamates decompose in acid solution and oxidations were consequently performed only on the anionic forms in the pH range 9-12, at which no change in rate constants was observed. The only exception was that of thiophenol, which, upon reacting with [Mo(CN)g] , showed that the reaction rate contribution due to oxidation of the PhSH form was less than 0.002% that of PhS . All of the dithiocarbamates obeyed a simple second-order rate law. 

Collman and Buckingham (1963) have reported preliminary results of studies on the hydrolytic cleavage of amino-terminal peptide bonds by m-hydroxyaquotriethylenetetraaminecobalt(III) ions. The amino-terminal residues of di- and tripeptides are selectively hydrolyzed by one equivalent of metal chelate and are converted to an inert metal complex. The reaction proceeds as shown on p. 63. 

Leaving Groups on Inert Metal Complexes with Inherent or Induced Lability Geoffrey A. Lawrance... 

LEAVING GROUPS ON INERT METAL COMPLEXES WITH INHERENT OR INDUCED LABILITY... 

Lability for at least one coordination site has been adequately demonstrated in the traditionally inert metal complexes in recent decades. Induction of lability by chemical reactions on a normally poor leaving group, by metal ions, protons, and base and by polyelectrolytes and micelles, offer opportunities in specific circumstances. Largely during the last decade, however, a number of ligands have appeared that are poor nucleophiles and inherently labile. Such molecules, of which tri-fluoromethanesulfonate is the most extensively studied, are univer-... 

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