Abstract
The catalytic activity of nickel complexes in hydrophosphination involving secondary phosphines is not a commonly studied transformation. Beyond a small number of stand-out examples, many reports in the literature focus on the use of simple nickel salts. β-Diketiminates have been proven to be incredibly effective ligands for catalysis using a range of metal centers. This synthetic study investigates the catalytic ability of a Ni(II) β-diketiminate complex in the hydrophosphination of alkenes and alkynes, with a serendipitous discovery of its ability to effect alkyne cyclotrimerization and phosphine dehydrocoupling.
Highlights
Transition metal catalyzed hydrophosphination is an economical route for atoms to access a range of functionalized phosphines from alkenes and alkynes [1,2,3]
We have already demonstrated the efficacy of β-diketiminate iron catalysts in hydrophosphination [4,5], and questioned whether, given the ease with which these complexes can be synthesized, the reactivity could be extended to other first row transition metal β-diketiminate complexes
In our previous studies of alkyne hydrophosphination we found that an iron–alkynyl complex was not a good catalyst [5]
Summary
Transition metal catalyzed hydrophosphination is an economical route for atoms to access a range of functionalized phosphines from alkenes and alkynes [1,2,3]. Nickel is an ideal metal to choose for this purpose: Holland has described an easy, scalable synthetic route to the N(SiMe3 )2 -ligated complex (1) [6]. Accessing a nickel complex that is a low coordinate with a σ-bound co-ligand should give high levels of reactivity via a σ-bond metathesis-type pathway. This hydrophosphination catalyzed by nickel is surprisingly underexplored [7]. The authors subsequently explored the effects of counterion, the full substrate scope and performed a detailed mechanistic study [9]
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