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Unexpected formation and conversion: role of substituents of 1,3-ynones on the reactivity and product distribution during their reactions with Ru3(CO)12

Abstract

The reactions of Ru3(CO)12 with alkynyl ketones R1C≡CC(O)R2 (R1=Et, R2=Me (1); R1=Ph, R2=Me (2); R1=n-hexyl, R2=Ph (3); R1=H, R2=CH3 (4); R1=C(O)OCH3, R2=OCH3 (5)) proceeds in toluene with the formation of three ruthenoles (1a-3a), four CO-inserted binuclear clusters (1b-2b, 1c and 3c), a tetranuclear cluster 4a, a binuclear cluster 5a and a cyclotrimerization product 5b. Clusters 1a-3a, 1b, 2b, 1c and 3c were isolated from the reactions of Ru3(CO)12 with two equivalents of the corresponding ketones 1-3; 4a and 5a were collected by adding 4 and 5 to Ru3(CO)12 in molar ratios of 1:1 and 1:3, respectively; 5b was obtained by adding 5 to 5a in molar ratio of 2:1. All compounds were characterized by NMR, FT-IR, MS-ESI and most of them were structurally verified by single crystal X-ray diffraction. Although the reaction products of 1-3 and Ru3(CO)12 exhibit similar cluster frameworks of usual ruthenoles and CO-inserted binuclear clusters, the isolation of the clusters 1b-2b, 1c and 3c reveals a strong dependence of them on both electronic and steric effects of substituents of the 1,3-ynones 1-3. In addition, detailed investigations suggested that high reactivity of the terminal hydrogen atom and electron-withdrawing property of the carbonyl group in 4 play a key role for the formation of 4a, and that structurally unusual 5a is an intermediate in the formation of 5b.

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Publication details

The article was received on 02 Nov 2018, accepted on 06 Dec 2018 and first published on 06 Dec 2018


Article type: Paper
DOI: 10.1039/C8NJ05573D
Citation: New J. Chem., 2018, Accepted Manuscript
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    Unexpected formation and conversion: role of substituents of 1,3-ynones on the reactivity and product distribution during their reactions with Ru3(CO)12

    L. Xu, L. Jiang, S. Li, G. Zhang, W. Zhang and Z. Gao, New J. Chem., 2018, Accepted Manuscript , DOI: 10.1039/C8NJ05573D

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