Reaction of Sulfur and Oxygen-Bridged 8-Quinolinolato Trinuclear Molybdenum Cluster [Mo3OS3(qn)3(H2O)3]+ with Acetylene Carboxylic Acids |
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Authors: | Kentaro Takano Hideki Kawasaki Genta Sakane Takashi Shibahara |
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Affiliation: | (1) Department of Chemistry, Okayama University of Science, Ridai-cho, Okayama 700-0005, Japan |
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Abstract: | The reaction of a sulfur and oxygen-bridged 8-quinolinolato trinuclear molybdenum cluster [Mo3OS3(qn)3(H2O)3]+ (3; Hqn = 8-quinolinol) with equimolar amounts of acetylene carboxylic acid, 4-pentynoic acid, 5-hexynoic acid, acetic acid, and pimelic acid gave clusters having μ-carboxylato groups, [Mo3OS3(qn)3(H2O)(μ-HC≡CCOO)] (6), [Mo3OS3(qn)3(H2O)(μ-HC≡C(CH2)2COO)] (7), [Mo3OS3(qn)3(H2O)(μ-HC≡C(CH2)3COO)] (8), [Mo3OS3(qn)3(H2O)(μ-CH3COO)] (4), and [{Mo3OS3(qn)3(C2H5OH)}2(μ-C7H10O4)] (5), respectively. X-ray structural analyses, 1H NMR, and electronic spectra of these clusters made clear that each of the COO− groups of the reagents bridges two Mo atoms in each cluster and that no adduct formation occurred at the sulfurs in the clusters. The reaction of 3 with a large excess-molar amount (50 times) of acetylene carboxylic acid gave [Mo3OS(μ3-SCH=C(COOH)S)(qn)3(H2O)(μ-HC≡CCOO)] (9) with two molecules of acetylene carboxylic acid, one acting as a carboxylato bridge and the other in adduct formation, as supported by the electronic and 1H NMR spectra. The corresponding aqua cluster [Mo3OS3(H2O)9]4+ (1), on the contrary, reacts with acetylene carboxylic acid to give adduct [Mo3OS(μ3-SCH=C(COOH)S)(H2O)9]4+ (2). Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. |
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Keywords: | 8-Quinolinol Trinuclear molybdenum cluster Acetylene carboxylic acid C– S bonds μ -Carboxylato groups |
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