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Construction of a monoanionic S,N,S-pincer ligand with a pyrrole core by sequential [1,2] phospho-Fries rearrangement. Characterization of palladium and silver coordination complexes

Abstract : The synthesis of an S,NH,S-pincer ligand possessing a pyrrole core and two O,O-diethylthiophosphonyl groups to design P[double bond, length as m-dash]S lateral coordination sites is reported. The synthetic procedure to produce this ligand makes use of the nitrogen atom of the pyrrole heterocycle to successively functionalize the ortho-positions with the two O,O-diethylthiophosphonyl moieties. The ortho-functionalization arises from a repetition of a [1,2] base-induced rearrangement allowing the transformation of O,O-diethyl-N-pyrollylthiophosphoramidate to ortho-thiophosphonate. The coordination properties of this tridentate S,NH,S-ligand have been investigated with silver and palladium metals. Reaction of the monoanionic S,N,S-pincer ligand 4 (O,O,O,O-tetraethylpyrrol-2,5-yl-dithiophosphonate) with PdCl2(MeCN)2 at room temperature in the presence of triethylamine gives rise to the formation of the η3-complex [Pd(η3-4′)Cl] 5. Ligand 4 also reacts with silver oxide in dichloromethane to produce complex 6 which, in the solid state, exists as a tetramer involving an almost linear arrangement of four silver atoms.
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https://hal.univ-brest.fr/hal-01577325
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Submitted on : Friday, August 25, 2017 - 2:34:11 PM
Last modification on : Tuesday, August 13, 2019 - 10:16:02 AM

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Aurore Fraix, Martin Lutz, Anthony L. Spek, Robertus J. M. Klein Gebbink, Gerard van Koten, et al.. Construction of a monoanionic S,N,S-pincer ligand with a pyrrole core by sequential [1,2] phospho-Fries rearrangement. Characterization of palladium and silver coordination complexes. Dalton Transactions, Royal Society of Chemistry, 2010, 39 (11), ⟨10.1039/B923351B⟩. ⟨hal-01577325⟩

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