Homo- and heterometallic chiral dynamic architectures from allyl–palladium(ii) building blocks

Abstract

New chiral tetranuclear square-like homo- and heterometallamacrocycles containing allyl–palladium and either {Pd(P–P)*} or {Pt(P–P)*} optically pure moieties (P–P* = (2S,3S)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphanyl)butane ((S,S)-DIOP) and (2S,4S)-2,4-bis(diphenylphosphanyl)pentane ((S,S)-BDPP)) have been obtained by the self-assembly of [Pd(η³-2-Me-C₃H₄)(4-PPh₂py)₂]⁺ and [M(P–P)*(H₂O)₂]²⁺ building blocks in a 1 : 1 molar ratio. The supramolecular assemblies thus prepared [{Pd(η³-2-Me-C₃H₄)}₂(4-PPh₂py)₄{M(P–P)*}₂](CF₃SO₃)₆ (M = Pd, Pt) have been fully characterised by multinuclear NMR spectroscopy and MS spectrometry. The structures display remarkable differences on their dynamic behaviour in solution that depend on the lability and thermodynamic strength of M–py bonds. The structural characteristics of the new metallamacrocyles obtained have also been unambiguously established by XRD analysis. The architectures have been assayed as catalytic precursors in the asymmetric allylic alkylation reaction.