Abstract
Developments in the confinement of phosphines within micro- or nano-environments are explored. Phosphines are ubiquitous across metal coordination chemistry and underpin some of the most famous homogeneous transition metal catalysts. Constraining phosphines within confined environments influences not only their behaviour but also that of their metal complexes. Notable examples include the use of metal-organic frameworks (MOFs) or metal-organic cages (MOCs) to support phosphines which demonstrate how the microenvironment within such constructs leads to reactivity modification. The development of phosphine confinement is explored and parallels are drawn with related constrained macrocyclic systems and mechanically interlocked molecules. The review concludes by identifying areas that remain a challenge and those that will provide new avenues for research.
Highlights
Owing to coordination incompatibility between hard Zr4+ ions and soft phosphine groups, the reaction of ZrCl4 with a triarylphosphine linker functionalised with three carboxylic acids (e.g. L6) yields a metal–organic frameworks (MOFs) (Zr-PMOF) with Zr–oxo secondary building units (SBUs) and uncoordinated, free phosphines which point into the pores, poised for further reactivity.[44,45]
The recyclability of the catalyst could be demonstrated as the powder X-ray diffraction (PXRD) of BINAP-MOF-Rh recovered from an AlMe3 addition reaction was the same as the freshly prepared sample, and its reuse in consecutive reactions resulted in only small decreases in activity and enantioselectivity
The presence of two distinct active sites within SulP1MOF-808(Hf)-Ir allow the system to be exploited as a high-performance bifunctional catalyst for the reductive amination of a range of ketones, since imine formation is catalysed by the framework metal cations, and hydrogenation is catalysed at the tethered Ir centre.[53]
Summary
Pilgrim ship, studying metal–organic cages with Jonathan Nitschke and was subsequently awarded a Royal Commission for the Exhibition of 1851 Research Fellowship His current research interests include supramolecular catalysis, developing responsive supramolecular systems, and designing new synthetic routes to interlocked molecules. In this review we will focus on phosphorus in well-defined artificial microenvironments and survey the structural and functional roles it plays and how these roles are influenced by the nature of the environment itself. This includes macromolecular structures such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), as well as discrete structures such as metal–organic cages (MOCs), organic macrocycles, and mechanically interlocked architectures such as rotaxanes and catenanes. In this review we will focus our discussion on phosphorus with three bonds to carbon or hydrogen, will consider some derivatives or closely related compounds where relevant
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