Journal
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
Volume 74, Issue 10, Pages 1927-1937Publisher
CHEMICAL SOC JAPAN
DOI: 10.1246/bcsj.74.1927
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Oxidative addition reactions of allylic halides, acetates, and carbonates with [Ru(eta (5)-C5Me5)(eta -amidinate)] [amidinate: (PrNC)-Pr-i(Me)=(NPr)-Pr-i (1a), (BuNC)-Bu-t(Ph)=(NBu)-Bu-t (1b)], which shows signs of coordinative unsaturation, gave novel cationic pi -allyl ruthenium(IV) species. The compounds [Ru(eta (3)-allyl)(eta (5)-C5Me5)(eta (2)-amidinate)]X-+(-) were isolated by anion exchange of the products (X = PF6, BF4, BPh4), and were characterized by spectroscopic analysis. The crystallography of two of the [Ru(eta (3)-allyl)(eta (5)-C5Me5)(eta (2)-amidinate)]X-+(-) revealed a four-legged piano stool structure in which two nitrogen atoms in the amidinate ligand and two carbon atoms in the eta (3)-allyl ligands occupy the positions of four legs; the orientation of the eta (3)-allyl ligand was endo. Although cyclic voltammograms of the precursor, [Ru(eta -C5Me5)(eta -amidinate)], indicated possible oxidative addition of organic halides other than allylic halides to [Ru(eta (5)-C5Me5)(eta -amidinate)], only allylic halides gave the corresponding Ru(IV) products. The importance of prior coordination of the carbon-carbon double bond of allylic substrates was evidenced by NMR observation of the intermediate in the reaction of la or lb with allyl acetate. Addition of nucleophiles such as PhLi, dimethyl methylsodiomalonate, and piperidine to the [Ru(eta (3)-allyl)(eta (5)-C5Me5)(eta (2)-amidinate)]X-+(-) gave rise to allylation of these nucleophiles and regeneration of [Ru(eta (5)-C5Me5)(eta -amidinate)]. The reactions of allyl methyl carbonate with nucleophiles were also achieved by catalysis of either [Ru(eta (5)-C5Me5)(eta -amidinate)] or [Ru(eta (3)-allyl)(eta (5)-C5Me5)(eta (2)-amidinate)]X-+(-).
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