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Issue 14, 2018
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Reaction of carbonyl trinuclear clusters with 2,5-bis(2-thienyl)-1-phenyl-phosphole as a ligand: a new pathway to ruthenacyclopentadiene and cyclopentadienone ruthenium complexes

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Abstract

[Ru3(CO)12] reacts with 2,5-bis(2-thienyl)-1-phenyl-phosphole (btpp) in refluxing CH2Cl2 to afford mono-, di- and trisubstituted derivatives: [Ru3(CO)11(btpp)] (1), [Ru3(CO)10(btpp)2] (2) and [Ru3(CO)9(btpp)3] (3), as well as the unique ruthenacyclopentadiene compound [Ru2(CO)4(μ-CO)(btpp)(μ-η114-C16H14S2)] (4), whose structure was confirmed by single-crystal X-ray crystallography. The photolysis of 3 in CH2Cl2 leads to the novel complex [Ru(CO)2(btpp)(η4-COC16H14S2)] (5), such that its single-crystal structure reveals the fragmentation of the triruthenium cluster, leading to a cyclopentadienone ruthenium complex. The synthesis of both ruthenacyclopentadiene (4) and cyclopentadienone (5) ruthenium complexes opens access to inaccessible ligand systems with π-conjugated structures that might be interesting in the development of new organometallic materials. The reaction of [Os3(CO)10(CH3CN)2] with btpp in refluxing CH2Cl2 affords mono- and disubstituted clusters: [Os3(CO)11(btpp)] (6) and [Os3(CO)10(btpp)2] (7). The trisubstituted complex [Os3(CO)9(btpp)3] (8) is formed by reaction of compound 7 with equimolar amounts of trimethylamine oxide and btpp. In contrast to 3, no fragmentation product was detected from the triosmium carbonyl cluster [Os3(CO)9(btpp)3] (8). A comparative analysis of the UV-vis spectra of [Ru3(CO)9(btpp)3] (3) and [Os3(CO)9(btpp)3] (8) suggests that their different photochemical reactivities might not only be affected by the energetics of their electronic transitions, but also by a combination of subsequent metal–ligand and metal–metal intramolecular interactions.

Graphical abstract: Reaction of carbonyl trinuclear clusters with 2,5-bis(2-thienyl)-1-phenyl-phosphole as a ligand: a new pathway to ruthenacyclopentadiene and cyclopentadienone ruthenium complexes

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Publication details

The article was received on 23 Mar 2018, accepted on 19 Jun 2018 and first published on 27 Jun 2018


Article type: Paper
DOI: 10.1039/C8NJ01442F
Citation: New J. Chem., 2018,42, 12234-12242
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    Reaction of carbonyl trinuclear clusters with 2,5-bis(2-thienyl)-1-phenyl-phosphole as a ligand: a new pathway to ruthenacyclopentadiene and cyclopentadienone ruthenium complexes

    Y. Otero, D. Peña, C. Lescop, E. Ávila, A. Arce, M. Hissler, R. Réau and R. Machado, New J. Chem., 2018, 42, 12234
    DOI: 10.1039/C8NJ01442F

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