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Cavitand Scission by Transition-Metal Centres – Cleaved Cavitand Chirality and Its Consequences

Abstract : Two molecules of the phosphine cavitand 5-diphenylphosphanyl-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene (1) each underwent cleavage of an O–CH2O bond when treated with 1 equiv. of [Ni(η5-C5H5)(1,5-cyclooctadiene)]BF4 to form a bis(phosphino–phenolato) complex (2) without a cyclopentadienyl ligand. The partially cleaved (P,O) ligands in 2 are chiral, and a single-crystal X-ray structure determination of 2 has shown that the complex molecule has close to twofold rotational symmetry with both ligand units in the same absolute configuration. As expected, the primary coordination sphere has a cis-NiO2P2 geometry. In contrast, C–O bond breaking occurred only once per metal centre when 1 was treated with [RuBr2(p-cymene)]2. This led to a crystallographically characterised complex [RuBr(P,O)(p-cymene)] (4) along with a minor amount of a species (5) that is assumed to be a stereoisomer. Upon crystallisation of 4, two distinct types of crystals were isolated from the same solution; some of these were the racemic compound, while the others were the racemic conglomerate
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01259514
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Submitted on : Wednesday, January 20, 2016 - 3:27:12 PM
Last modification on : Thursday, April 23, 2020 - 2:26:29 PM

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Thierry Chavagnan, David Semeril, Dominique Matt, Loic Toupet, Jack Harrowfield, et al.. Cavitand Scission by Transition-Metal Centres – Cleaved Cavitand Chirality and Its Consequences. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2016, 2016 (4), pp.497-502. ⟨10.1002/ejic.201501089⟩. ⟨hal-01259514⟩

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