Issue 30, 2017

Calix[4]arene-fused phospholes

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

Supplementary files

Article information

Article type
Paper
Submitted
26 May 2017
Accepted
21 Jun 2017
First published
06 Jul 2017

Dalton Trans., 2017,46, 9833-9845

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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