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Issue 44, 2018
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Diverse modes of functionalisation of ruthenium coordinated β-ketoiminate analogues

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Abstract

This article compares the reactivity patterns of β-ketoiminate (AcNac) and β-thioacetyliminate (SacNac), with special reference to the unsymmetrical β-diketiminate (NacNac), on the selective {Ru(acac)2} metal platform that encompasses the electronically rich acac (= acetylacetonate) moiety. In this regard, structural and spectroelectrochemical aspects have been reported for the newly designed complexes [RuIII(acac)2(AcNacR)] (1a–1c), [RuIII(acac)2(SacNacH)] (2) and [RuIII(acac)2(NacNacR)] (3a–3c) [R = para-substituents (H, Cl, OMe) of the N-bearing aryl group]. The subsequent exploration of the impact of metal chelation on the reactivity profile of the β-ketoiminate analogues revealed the following: (a) the facile oxygenation of the methine centre (Cβ–H) of the unsymmetrical NacNac in 3 led to ketodiimine (L1) in [RuII(acac)2(L1)] (4), while analogues AcNac and SacNac in 1 and 2, respectively, remained resistant to oxidative functionalisation due to their relatively lower charge densities at the methine (Cβ) centres. (b) Hydrolysis of the relatively weak C–S bond of SacNac resulted in a μ3-S bridged [{Ru(acac)2}33-S)] complex (2′). (c) Unlike 2 and 3, AcNac in 1 underwent an interesting transformation selectively in a non-polar solvent (toluene) to the 3-acetyl AcNac (L2) moiety in 5 ([RuIII(acac)2(L2)]) via the generation of a new C–C bond at its backbone, indicating the ambiphilic feature of AcNac. The paper also addresses the aforesaid transformation processes and fractional redox non-innocence of AcNac, SacNac and NacNac in 1n, 2n and 3n (n = +1, 0, −1), respectively.

Graphical abstract: Diverse modes of functionalisation of ruthenium coordinated β-ketoiminate analogues

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Publication details

The article was received on 19 Jul 2018, accepted on 18 Oct 2018 and first published on 19 Oct 2018


Article type: Paper
DOI: 10.1039/C8DT02940G
Citation: Dalton Trans., 2018,47, 15897-15906
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    Diverse modes of functionalisation of ruthenium coordinated β-ketoiminate analogues

    S. K. Bera, S. Panda, S. Dey Baksi and G. K. Lahiri, Dalton Trans., 2018, 47, 15897
    DOI: 10.1039/C8DT02940G

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