TY - JOUR
T1 - Oxidative addition of allylic substrates to coordinatively unsaturated ruthenium compounds, [Ru(η 5-C 5Me 5)(η-amidinate)]
T2 - Preparation, structure elucidation, and catalysis of novel ruthenium (IV)-η 3-allyl complexes
AU - Kondo, Hideo
AU - Kageyama, Akira
AU - Yamaguchi, Yoshitaka
AU - Haga, Masa Aki
AU - Kirchner, Karl
AU - Nagashima, Hideo
PY - 2001/10/1
Y1 - 2001/10/1
N2 - Oxidative addition reactions of allylic halides, acetates, and carbonates with [Ru(η 5-C 5Me 5)(η-amidinate)] [amidinate: iPrNC(Me)=N iPr (1a), 1BuNC(Ph)=N 1Bu (1b)], which shows signs of coordinative unsaturation, gave novel cationic π-allyl ruthenium(IV) species. The compounds [Ru(η 3-allyl)(η 5-C 5Mes)(η 2-amidinate)] +X - were isolated by anion exchange of the products (X = PF 6, BF 4, BPh 4), and were characterized by spectroscopic analysis. The crystallography of two of the [Ru(η 3-allyl)(η 5-C 5Mes)(η 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 η 3-allyl ligands occupy the positions of four legs; the orientation of the η 3-allyl ligand was endo. Although cyclic voltammograms of the precursor, [Ru(η 5-C 5Me 5)(η-amidinate)], indicated possible oxidative addition of organic halides other than allylic halides to [Ru(η 5-C 5Me 5)(η-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 1a or 1b with allyl acetate. Addition of nucleophiles such as PhLi, dimethyl methylsodiomalonate, and piperidine to the [Ru(η 3-allyl)(η 5-C 5Me 5)(η 2-amidinate)] +X - gave rise to allylation of these nucleophiles and regeneration of [Ru(η 5-C 5Me 5)(η-amidinate)]. The reactions of allyl methyl carbonate with nucleophiles were also achieved by catalysis of either [Ru(η 5C 5Me 5)(η-amidinate)] or [Ru(η 3-allyl)(η 5-C 5Me 5)(η 2-amidinate )]+X -.
AB - Oxidative addition reactions of allylic halides, acetates, and carbonates with [Ru(η 5-C 5Me 5)(η-amidinate)] [amidinate: iPrNC(Me)=N iPr (1a), 1BuNC(Ph)=N 1Bu (1b)], which shows signs of coordinative unsaturation, gave novel cationic π-allyl ruthenium(IV) species. The compounds [Ru(η 3-allyl)(η 5-C 5Mes)(η 2-amidinate)] +X - were isolated by anion exchange of the products (X = PF 6, BF 4, BPh 4), and were characterized by spectroscopic analysis. The crystallography of two of the [Ru(η 3-allyl)(η 5-C 5Mes)(η 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 η 3-allyl ligands occupy the positions of four legs; the orientation of the η 3-allyl ligand was endo. Although cyclic voltammograms of the precursor, [Ru(η 5-C 5Me 5)(η-amidinate)], indicated possible oxidative addition of organic halides other than allylic halides to [Ru(η 5-C 5Me 5)(η-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 1a or 1b with allyl acetate. Addition of nucleophiles such as PhLi, dimethyl methylsodiomalonate, and piperidine to the [Ru(η 3-allyl)(η 5-C 5Me 5)(η 2-amidinate)] +X - gave rise to allylation of these nucleophiles and regeneration of [Ru(η 5-C 5Me 5)(η-amidinate)]. The reactions of allyl methyl carbonate with nucleophiles were also achieved by catalysis of either [Ru(η 5C 5Me 5)(η-amidinate)] or [Ru(η 3-allyl)(η 5-C 5Me 5)(η 2-amidinate )]+X -.
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U2 - 10.1246/bcsj.74.1927
DO - 10.1246/bcsj.74.1927
M3 - Article
AN - SCOPUS:0035149946
VL - 74
SP - 1927
EP - 1937
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 10
ER -