Synthesis and reactivity of main-group complexes with heteroatomic double bonds

Thesis

The synthesis and reactivity of compounds containing heteroatomic double bonds are described in this thesis. An overview of multiple bonds between heavier p-block elements is presented in Chapter 1, including the general synthetic routes for the formation of homoatomic and heteroatomic main group multiple bonds. The formation of group 15–element double bonds from azides and phosphaketenes is also outlined.

Chapter 2 describes the synthesis of phosphagallenes through the decarbonylation of phosphaketenes. Attempts at forming analogous iminogallenes are also described herein.

Chapter 3 explores the reactivity of a phosphanyl phosphagallene towards small molecules such as H2, CO2 and E–H substrates. Two different reaction pathways were found for the activation of amines, both of which were investigated by Density Functional Theory calculations.

Chapter 4 expands on the synthesis of group 15–element double bonds by demonstrating the synthesis of Ge=P and Sn=P double bonds. Additionally, the reactivity of a phosphanyl phosphagermene with CO2, amines and silanes is described.

Finally, Chapter 5 discusses the aim of using compounds with multiple bonds between the heavier main group elements in order to catalyse the hydroamination of substrates. Two different catalyst designs containing transition metals are targeted: a transition metal- phosphinidene complex and a transition metal substituted phosphagallene. The attempted synthesis of these compounds is described.

Authors: Feld, J

• DOI: 10.5287/ora-zbmvznp69
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: multiple bond; gallium; main group; Small molecule activation; Frustrated Lewis Pair; tin; germanium; double bond; phosphorus; phosphinidene
• Subjects: Inorganic compounds--Synthesis; Chemistry, Inorganic