Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 3, 2019
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

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., 2019,43, 1478-1486

  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements