Issue 25, 2019

Barium complexes with crown-ether-functionalised amidinate and iminoanilide ligands for the hydrophosphination of vinylarenes

Abstract

The detailed multistep syntheses of two nitrogen-based sterically congested iminoanilidine and amidine proligands bearing a tethered 15-member aza-ether-crown macrocycle, namely {I^Acrown}H and {Amcrown}H, are reported. These proligands react with [Ba{N(SiMe2H)2}2·(thf)n] to generate the heteroleptic barium complexes [{I^Acrown}BaN(SiMe2H)2] (5) and [{Amcrown}BaN(SiMe2H)2] (6) in high yields. These complexes exhibit high coordination numbers (resp. eight and seven) and are in addition stabilised by mild Ba⋯H–Si interactions. Unusually for oxophilic elements such as barium, the amidinate ligand in 6 is only η1-coordinated. Complexes 5 and 6 mediate the intermolecular hydrophosphination of styrene with primary (PhPH2) and secondary (HPPh2) phosphines. Their catalytic performance compares favourably with those of other barium precatalysts for these reactions. During the course of the hydrophosphination of styrene with HPPh2 catalysed by 5, the phosphide complex [{I^Acrown}BaPPh2] (7) could be intercepted and crystallographically characterised.

Graphical abstract: Barium complexes with crown-ether-functionalised amidinate and iminoanilide ligands for the hydrophosphination of vinylarenes

Supplementary files

Article information

Article type
Paper
Submitted
09 Ebr. 2019
Accepted
13 Mae 2019
First published
14 Mae 2019

Dalton Trans., 2019,48, 9173-9180

Barium complexes with crown-ether-functionalised amidinate and iminoanilide ligands for the hydrophosphination of vinylarenes

E. Le Coz, H. Roueindeji, T. Roisnel, V. Dorcet, J. Carpentier and Y. Sarazin, Dalton Trans., 2019, 48, 9173 DOI: 10.1039/C9DT01512D

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