Azophosphines: synthesis, coordination chemistry and catalysis

Jordan-Rose, Emma Jane ORCID: 0009-0005-5440-0418 (2025). Azophosphines: synthesis, coordination chemistry and catalysis. University of Birmingham. Ph.D.

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Abstract

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. Azophosphines, the phosphorus-containing analogues of triazenes, are underexplored but offer great potential as flexible and small bite-angle ligands.
Chapter 1 introduces the concept of phosphorus-analogues of common functional groups and considers the application of azophosphines as novel hybrid ligands.
Chapter 2 explores the synthesis and characterisation of a family of air-stable azophosphine-borane complexes, and their subsequent deprotection to the free azophosphines.
Chapter 3 demonstrates that the azophosphine synthesis can tolerate substituents with strongly electron-donating and electron-withdrawing para-Z groups and that the nature of this Z group can affect the spectroscopic and structural properties of the azophosphines. Highlighted is the availability of the phosphorus lone pair for coordination. Azophosphines are shown to be relatively weak phosphine donors, but the donor properties can be fine-tuned within this area of chemical space.
Chapter 4 provides evidence for this by demonstrating that neutral azophosphines can coordinate as ligands to a range of transition metal centres, with a focus on Ru(II) and Au(I) complexes, and can coordinate as monodentate, bidentate or bridging ligands in a controlled manner, in contrast to their nitrogen analogues.
Chapter 5 describes the culmination of the research on azophosphines presented in this thesis in the first use of the Ru- and Au-azophosphine complexes as catalysts in which additive-free transformations were achieved.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):