Homo- and heterometallic chiral dynamic architectures from allyl–palladium(ii) building blocks. Issue 15 (29th March 2022)

• Record Type: Journal Article
• Authors: Ferrer, Montserrat; Gallen, Albert; Martínez, Manuel; Rocamora, Mercè; Puttreddy, Rakesh; Rissanen, Kari
• Is Part Of: Dalton transactions. Volume 51:Issue 15(2022)
• Page Start: 5913
• Page End: 5928
• Publication Date: 2022-03-29
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt03706d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Allyl–palladium chiral metallamacrocycles were prepared by self-assembly reactions. Their dynamic behaviour and catalytic activity in the allylic alkylation reaction were investigated. 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 (2 S, 4 S )-2, 4-bis(diphenylphosphanyl)pentane (( S, S )-BDPP)) have been obtained by the self-assembly of [Pd(η 3 -2-Me-C3 H4 )(4-PPh2 py)2 ] + and [M(P–P)*(H2 O)2 ] 2+ building blocks in a 1 : 1 molar ratio. The supramolecular assemblies thus prepared [{Pd(η 3 -2-Me-C3 H4 )}2 (4-PPh2 py)4 {M(P–P)*}2 ](CF3 SO3 )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.