Abstract

AbstractHerein we report the synthesis of three heteroleptic first‐row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)‐carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt‐catalysed hydrophosphination process that solely and selectively yields the β addition (anti‐Markovnikov) product. The scope of this transformation has been investigated using a variety of activated alkenes. Isolation and characterisation of substrate‐coordinated intermediates reveal available coordination sites, which provide insight into the proposed catalytic cycle.magnified image

Highlights

  • Phosphorus-containing compounds are a precious commodity, finding use in numerous areas such as organocatalysis,[1] bulk and fine chemical production,[2] and the pharmaceutical industry.[3]

  • Abstract: we report the synthesis of three heteroleptic first-row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)-carbonyl complexes via a reductive carbonylation route

  • Following our previous report, which detailed the use of low-coordinate transition metal precatalysts in the hydrophosphination of isocyanates,[4] we looked to extend our studies to other unsaturated substrates

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Summary

Introduction

Phosphorus-containing compounds are a precious commodity, finding use in numerous areas such as organocatalysis,[1] bulk and fine chemical production,[2] and the pharmaceutical industry.[3]. Of special interest is the hydrophosphination of olefins and alkynes, which has received much attention in the last two decades.[5,6,7,8,9,10,11] The potential for accessing atomefficient transformations involving regio- and stereoselective processes has, in turn, driven advances for metal-catalysed hydroelementation reactions. This has been revitalised by the development of tailored catalyst design; a core area for regioselective metal-catalysed hydrophosphination (Scheme 1). The quest for cheaper, earth-abundant, non-toxic catalysts for hydrophosphination and other hetero-atom insertion processes, involving iron,[5,6,9,16,17,18,19,20,21,22,23,24,25] cobalt,[26,27,28,29,30,31] and manganese[32] is of continuing importance

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