Synthesis and characterisation of saturated and unsaturated triruthenium clusters containing electronically symmetrical and asymmetrical alkynes

Reaction of FcCCC(O)R (Fc = ferrocenyl) with Ru3(CO)12 leading to unexpected nitro-group reduced ruthenoles and 1,2-CO-inserted triruthenium clusters

“…In recent years, some carbonyl ruthenium compounds formed via Ru 3 (CO) 12 and unsaturated hydrocarbons have been used in catalytic reactions. 7 These reactions provide more possibilities for Ru 3 (CO) 12 to become a potential catalyst for the conversion of alkyne compounds.…”

“…10 In the meantime, S. W. Lau synthesized ruthenium diyne clusters with diverse Ru-diyne coordination modes via reaction of Ru 3 (CO) 12 with 1,4-bis(1-hydroxycyclopentyl)-1,3-butadiyne. 11 Then R. Rosseto systematically investigated the reaction of some asymmetrical alkynes with Ru 3 (CO) 12 and revealed the electron effects of the groups in the aromatic ring(s). 12 M. Li reported the trinuclear complexes (3,4-R 2 C 5 H 2 ) 2 (m 3 -C 4 Ph 2 ) Ru 3 (CO) 6 (m-CO) 2 (R ¼ Me, Ph) and the dinuclear complex (3,4-Ph 2 C 5 H 2 ) 2 (m-C 4 Ph 2 )Ru 2 (CO) 5 (m-CO) by reaction of Ru 3 (CO) 12 with {h 5 -[1,2-R 2 -4-(PhC^C)C 5 H 2 ]} 2 ZrCl 2 (R ¼ Me, Ph), via the unexpected cleavage of the two Cp-Zr bonds.…”

“…11 Then R. Rosseto systematically investigated the reaction of some asymmetrical alkynes with Ru 3 (CO) 12 and revealed the electron effects of the groups in the aromatic ring(s). 12 M. Li reported the trinuclear complexes (3,4-R 2 C 5 H 2 ) 2 (m 3 -C 4 Ph 2 ) Ru 3 (CO) 6 (m-CO) 2 (R ¼ Me, Ph) and the dinuclear complex (3,4-Ph 2 C 5 H 2 ) 2 (m-C 4 Ph 2 )Ru 2 (CO) 5 (m-CO) by reaction of Ru 3 (CO) 12 with {h 5 -[1,2-R 2 -4-(PhC^C)C 5 H 2 ]} 2 ZrCl 2 (R ¼ Me, Ph), via the unexpected cleavage of the two Cp-Zr bonds. 13 Recently, P. Mathur reported a series of [Ru(CO) 3 (h 4ruthenole)] derivatives during the reaction of Ru 3 (CO) 12 with FcC 2 C 2 Ph (Fc ¼ ferrocenyl).…”

“…13 Recently, P. Mathur reported a series of [Ru(CO) 3 (h 4ruthenole)] derivatives during the reaction of Ru 3 (CO) 12 with FcC 2 C 2 Ph (Fc ¼ ferrocenyl). 14 Therefore, the reactions of Ru 3 (CO) 12 with different acetylenes can afford a variety of unexpected products, [10][11][12][13][14][15] which motivates us to explore the activated mechanisms via experienced sophisticated transformations of alkynes.…”

“…17 Aer a detailed analysis of the results, we believed that, during the reaction of a 1,3-ynone with Ru 3 (CO) 12 , not only the group at its carbonyl side exerts effects on its reactivity and transformation process, but the group at its C^C side inuences the reaction direction as well. As a continuing work in the chemistry of Ru 3 (CO) 12 with alkynyl ketones, we introduced a ferrocenyl group at the C^C side of a 1,3-diphenylprop-2-yn-1-one derivative to substitute the phenyl group, and investigated the structures of the intermediates and nal products during its reactions with Ru 3 (CO) 12 .…”