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Issue 30, 2017
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Calix[4]arene-fused phospholes

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Abstract

An upper rim, o-(diphenylphosphinyl)phenyl-substituted calix[4]arene has been prepared and its coordinative properties investigated. When heated in the presence of palladium, the new biarylphosphine undergoes conversion into two diastereomeric, calixarene-fused phospholes. In both, the P lone pair adopts a fixed orientation with respect to the calixarene core. The more hindered phosphole (8), i.e. the one with the endo-oriented lone pair (cone angle 150°–175°), forms complexes having their metal centre positioned very near the calixarene unit but outside the cavity, thus inducing an unusual chemical shift of one of the methylenic ArCH2Ar protons owing to interactions with the metal centre. As expected for dibenzophospholes, the complex [Rh(acac)(CO)·8], when combined with one equivalent of free 8, efficiently catalyses the hydroformylation of styrene, the catalytic system displaying high regioselectivity in favour of the branched aldehyde (b/l ratio up to 30). The optical and redox properties of the derivatives have also been investigated.

Graphical abstract: Calix[4]arene-fused phospholes

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Publication details

The article was received on 26 May 2017, accepted on 21 Jun 2017 and first published on 06 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT01899A
Citation: Dalton Trans., 2017,46, 9833-9845
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    Calix[4]arene-fused phospholes

    F. Elaieb, D. Sémeril, D. Matt, M. Pfeffer, P. Bouit, M. Hissler, C. Gourlaouen and J. Harrowfield, Dalton Trans., 2017, 46, 9833
    DOI: 10.1039/C7DT01899A

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