Issue 3, 2019

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

Abstract

The reactions of Ru3(CO)12 with alkynyl ketones R1C[triple bond, length as m-dash]CC(O)R2 (R1 = Et, R2 = Me (1); R1 = Ph, R2 = Me (2); R1 = n-hexyl, R2 = Ph (3); R1 = H, R2 = CH3 (4); and 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 a molar ratio of 2 : 1. All compounds were characterized by NMR, FT-IR, and 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 their strong dependence on both electronic and steric effects of the substituents of the 1,3-ynones 1–3. In addition, detailed investigations suggested that the high reactivity of the terminal hydrogen atom and electron-withdrawing property of the carbonyl group in 4 play a key role in the formation of 4a, and that the structurally unusual 5a is an intermediate in the formation of 5b.

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

Supplementary files

Article information

Article type
Paper
Submitted
02 Nov 2018
Accepted
06 Dec 2018
First published
06 Dec 2018

New J. Chem., 2019,43, 1478-1486

Unexpected formation and conversion: role of substituents of 1,3-ynones in 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., 2019, 43, 1478 DOI: 10.1039/C8NJ05573D

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