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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.

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Supplementary files

Publication details

The article was received on 09 Apr 2019, accepted on 13 May 2019 and first published on 14 May 2019


Article type: Paper
DOI: 10.1039/C9DT01512D
Dalton Trans., 2019, Accepted Manuscript

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    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, Accepted Manuscript , DOI: 10.1039/C9DT01512D

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