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Issue 44, 2018
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Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles

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Abstract

Herein we report on the synthesis, characterization and the ensuing chemistry of iminophosphorane palladacycles. Treatment of Ph3P[double bond, length as m-dash]N-(2-OHC6H4), 1, with sodium tetrachloropalladate gives 2 with the ligand as terdentate [C,N,O] allowing for only one μ-Cl ligand bonding the metal centers, resulting in a dinuclear complex. Treatment of 2 with PPh3 gives the mononuclear complex 3, whereas the reaction of 2 with diphosphanes Ph2P(CH2)nPPh2 in 1 : 2 ratio gives mixtures of 4 and 5 (n = 2) and 6 and 7 (n = 3). From them, the mononuclear complexes 4 and 6, and the dinuclear compounds, 5 and 7, were obtained with the parent ligand as bidentate [C,N]. The former two are of zwitterionic nature void of any counterion, with the phosphane ligand in the chelating mode. In a remarkable case of chemical serendipity, a solution of 2 left to stand produced crystals of complex 8: this is the missing link in the series of triphenylphosphane chalcogenide metallacycles. The experiment is repeatable; however, direct metallation of triphenylphosphane oxide was not possible.

Graphical abstract: Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles

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Publication details

The article was received on 26 Jul 2018, accepted on 11 Oct 2018 and first published on 22 Oct 2018


Article type: Paper
DOI: 10.1039/C8DT03062F
Citation: Dalton Trans., 2018,47, 15801-15807
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    Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles

    A. Fernández-Figueiras, F. Lucio-Martínez, P. Munín-Cruz, P. Polo-Ces, F. Reigosa, H. Adams, M. T. Pereira and J. M. Vila, Dalton Trans., 2018, 47, 15801
    DOI: 10.1039/C8DT03062F

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