Synthesis and reactivity of phosphorus-boron multiple bonds
Price, Amy Nicole
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Phosphorus-boron multiple-bonds are of interest because of their predicted reactivity with small molecules; their potential as reagents for the synthesis of molecules isosteric to carbon analogues which exhibit conjugation; and because they have potential as nucleation sites for the solution-phase synthesis of boron phosphide. Phosphaborenes (RP=BR’) have not yet been reported due to their propensity to oligomerise to dimers or trimers, even with bulky and electronically-stabilising substituents upon phosphorus and boron. Base-stabilisation at boron allows the isolation of phosphaborenes by preventing oligomerisation, although this alters the reactivity of the phosphaborene unit. An alternative method of studying phosphaborenes free of base or acid coordination is via their thermal generation from a phosphaborene dimer and subsequent in situ reactions with suitable substrates. Chapter 1 examines the potential uses of phosphaborenes in the context of other low-valent main group molecules. The likely reactivity of phosphorus-boron multiple bonds is discussed in the context of the iminoboranes (RNBR’) and the isoelectronic heavier group 14 alkyne and alkene analogues. The use of unsaturated main group fragments to build molecular clusters is considered along with the potential role that phosphorus boron multiple bonds could play in preparing boron phosphide fragments. The uses and methods of preparation of group 13/15 containing molecules exhibiting conjugation are discussed, along with the possibility that phosphaborenes would be useful reagents to prepare new P-B/C-C isosteres. Chapter 2 looks at how base-promoted trimethylsilylchloride elimination can be used to prepare base-stabilised phosphaborenes from suitable precursors (RP(SiMe₃)B(X)R’ and the mechanism of these reactions. The reactivity of base-stabilised phosphaborenes with Lewis acids is also examined. Chapter 3 covers how base-promoted (L = base) trimethylsilyl halide abstraction from functionalised precursors ((Me₃Si)₃P·BBr₃) can be harnessed to prepare new functionalised phosphinoboranes ((Me₃Si)₂PB(L)Br₂) and phosphaborenes (Me₃SiP=B(L)Br). A 1-dihydro-2-dibromo functionalised phosphinoborane H₂PB(Br₂)L can be prepared from Me₃Si)₂PB(Br₂)L. A subsequent base-promoted dehydrohalogenation yields the hydro-bromo substituted phosphaborene HP=B(L)Br. Chapter 4 examines the in situ thermal generation of a phosphaborene generated from a phosphaborene dimer and its reactivity with bases and unsaturated organic molecules to prepare 1,2-phosphaboretes and 1,2-phosphaboretanes. Chapter 5 explores the diverse reactivity of the 1,2-phosphaboretes. 1,2- phosphaboretes are capable of FLP-like insertion reactions with an isonitrile and carbon monoxide. They are also ring-opened by the coordination of a Lewis acid or base to phosphorus or boron respectively to give P-B containing butadiene analogues. The reaction of the 1,2-phosphaborete with phenyl acetylene proceeds via an unusual carbon-carbon bond cleavage to generate the first example of a 1,3- phosphaborine benzene analogue, rather than the expected 1,4-phosphaborine.