TY - JOUR
T1 - Chemistry of coordinatively unsaturated organoruthenium amidinates as entry to homogeneous catalysis
AU - Nagashima, Hideo
AU - Kondo, Hideo
AU - Hayashida, Taizo
AU - Yamaguchi, Yoshitaka
AU - Gondo, Mitsuru
AU - Masuda, Satoshi
AU - Miyazaki, Kazuma
AU - Matsubara, Kouki
AU - Kirchner, Karl
N1 - Funding Information:
We thank financial support from Grant-in-Aid for Scientific Research (13029090 and 14044081). Technical assistance by Jun-ichi Terasawa to summarize this article is acknowledged.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2003/10
Y1 - 2003/10
N2 - The chemistry of coordinatively unsaturated organoruthenium complexes is reviewed in this article. In particular, the subject is focused on neutral and cationic organoruthenium amidinates, which formally have 16 valence electrons and show signs of coordinative unsaturation. The ruthenium amidinates, (η5-C5Me5)Ru(η-amidinate) (1), and their isoelectronic analogues, [η6-arene)Ru(η -amidinate)]+ (2), are synthesized and characterized; a possible stabilizing factor of the unsaturated metal center is weak coordination of π-electrons in the amidinates ligands. Reactions of various two-electron donor ligands with 1 or 2 reveal the strong w-donor property of 1 and Lewis acid nature of 2. One or two-electron redox processes of 1 in the reactions with organic halides are studied by isolation of the corresponding Ru(III) and Ru(IV) products; the results lead to their catalysis for the Tsuji-Trost reaction and the intramolecular Kharasch reaction. The treatment of 2 with trimethylsilyldiazomethane results in the formation of cationic amidinato-carbene complexes, which involve unusual reversible metal-to-carbon silyl group migration.
AB - The chemistry of coordinatively unsaturated organoruthenium complexes is reviewed in this article. In particular, the subject is focused on neutral and cationic organoruthenium amidinates, which formally have 16 valence electrons and show signs of coordinative unsaturation. The ruthenium amidinates, (η5-C5Me5)Ru(η-amidinate) (1), and their isoelectronic analogues, [η6-arene)Ru(η -amidinate)]+ (2), are synthesized and characterized; a possible stabilizing factor of the unsaturated metal center is weak coordination of π-electrons in the amidinates ligands. Reactions of various two-electron donor ligands with 1 or 2 reveal the strong w-donor property of 1 and Lewis acid nature of 2. One or two-electron redox processes of 1 in the reactions with organic halides are studied by isolation of the corresponding Ru(III) and Ru(IV) products; the results lead to their catalysis for the Tsuji-Trost reaction and the intramolecular Kharasch reaction. The treatment of 2 with trimethylsilyldiazomethane results in the formation of cationic amidinato-carbene complexes, which involve unusual reversible metal-to-carbon silyl group migration.
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U2 - 10.1016/S0010-8545(03)00124-3
DO - 10.1016/S0010-8545(03)00124-3
M3 - Article
AN - SCOPUS:0345275975
SN - 0010-8545
VL - 245
SP - 177
EP - 190
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
IS - 1-2
ER -