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Half-sandwich ruthenium(ii) complexes with tethered arene-phosphinite ligands: synthesis, structure and application in catalytic cross dehydrogenative coupling reactions of silanes and alcohols

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Abstract

The preparation of the tethered arene-ruthenium(II) complexes [RuCl261(P)-C6H5(CH2)nOPR2}] (R = Ph, n = 1 (9a), 2 (9b), 3 (9c); R = iPr, n = 1 (10a), 2 (10b), 3 (10c)) from the corresponding phosphinite ligands R2PO(CH2)nPh (R = Ph, n = 1 (1a), 2 (1b), 3 (1c); R = iPr, n = 1 (2a), 2 (2b), 3 (2c)) is presented. Thus, in a first step, the treatment at room temperature of tetrahydrofuran solutions of dimers [{RuCl(μ-Cl)(η6-arene)}2] (arene = p-cymene (3), benzene (4)) with 1-2a-c led to the clean formation of the corresponding mononuclear derivatives [RuCl26-p-cymene){R2PO(CH2)nPh}] (5-6a-c) and [RuCl26-benzene){R2PO(CH2)nPh}] (7-8a-c), which were isolated in 66–99% yield. The subsequent heating of 1,2-dichloroethane solutions of these compounds at 120 °C allowed the exchange of the coordinated arene. The substitution process proceeded faster with the benzene derivatives 7-8a-c, from which complexes 9-10a-c were generated in 61–82% yield after 0.5–10 h of heating. The molecular structures of [RuCl26-p-cymene){iPr2PO(CH2)3Ph}] (6c) and [RuCl261(P)-C6H5(CH2)nOPiPr2}] (n = 1 (10a), 2 (10b), 3 (10c)) were unequivocally confirmed by X-ray diffraction methods. In addition, complexes [RuCl261(P)-C6H5(CH2)nOPR2}] (9-10a-c) proved to be active catalysts for the dehydrogenative coupling of hydrosilanes and alcohols under mild conditions (r.t.). The best results were obtained with [RuCl261(P)-C6H5(CH2)3OPiPr2}] (10c), which reached TOF and TON values up to 117 600 h−1 and 57 000, respectively.

Graphical abstract: Half-sandwich ruthenium(ii) complexes with tethered arene-phosphinite ligands: synthesis, structure and application in catalytic cross dehydrogenative coupling reactions of silanes and alcohols

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Publication details

The article was received on 15 Nov 2019, accepted on 02 Dec 2019 and first published on 02 Dec 2019


Article type: Paper
DOI: 10.1039/C9DT04421C
Dalton Trans., 2020, Advance Article

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    Half-sandwich ruthenium(II) complexes with tethered arene-phosphinite ligands: synthesis, structure and application in catalytic cross dehydrogenative coupling reactions of silanes and alcohols

    R. González-Fernández, P. Crochet and V. Cadierno, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04421C

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