Ammines synthesis

The iridium(III) complexes are broadly similar to the rhodium(III) ammines a selection of synthesis is shown in Figure 2.84. 

A recently reported synthesis involves refluxing a mixture of IrCl3 and ethanoic acid with urea hydrolysis of the urea proceeds steadily generating the ammonia ligands. This resulting mixture of the penta-, tetra- and tri-ammines can be separated chromatographically [149],... 

Their synthesis uses H202 to carry out oxidative addition to platinum(II) ammines... 

Kolis et al. reported the synthesis of some metal sulfide salts of homolep-tic lanthanide ammine complexes using supercritical ammonia as a reaction medium (Scheme 12) [49]. They proposed that these reactions proceed via a... 

Mixed-valence complexes terminated in other than ammine and cyano ligands include [([9]aneS3)ClRu(/x-243)RuCl([9]aneS3)] which exhibits a strong intermetallic interaction consistent with a Robin-Day class III (delocalized) species. The synthesis of the Ru Ru complex [ P(OMe)3 2(MeCN)Ru(u-S2)(/u-NH2NH2)Ru P(OMe)3 2(MeCN)] + has been reported. Oxidation of the (M = Ru or Os) complexes [ 4 -(4-MeC6H4 tpy)M(u-L)M 4 -(4-... 

Alternative methods for the synthesis of mononuclear Os(VI) nitrido complexes are the chemical or electrochemical oxidation of Os(II) or Os(III) ammine complexes (41-43) and the oxidation of Os(IV) complexes by organic azides (44). 

Sargeson and his coworkers have developed an area of cobalt(III) coordination chemistry which has enabled the synthesis of complicated multidentate ligands directly around the metal. The basis for all of this chemistry is the high stability of cobalt(III) ammine complexes towards dissociation. Consequently, a coordinated ammonia molecule can be deprotonated with base to produce a coordinated amine anion (or amide anion) which functions as a powerful nucleophile. Such a species can attack carbonyl groups, either in intramolecular or intermolecular processes. Similar reactions can be performed by coordinated primary or secondary amines after deprotonation. The resulting imines coordinated to cobalt(III) show unusually high stability towards hydrolysis, but are reactive towards carbon nucleophiles. While the cobalt(III) ion produces some iminium character, it occupies the normal site of protonation and is attached to the nitrogen atom by a kinetically inert bond, and thus resists hydrolysis. 

It is noteworthy that the successful synthesis of nitrito-nitro linkage isomers for other metal ammines was designed only after the mechanism of formation of [Co(NH3)50NO]2+ and its rearrangement had been elucidated.4 It was found that the nitrito complex is readily formed without the cleavage of the Co—0 bond ... 

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