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Title: Synthesis and reactivity of low valent main-group compounds
Author: Millet, Clément René Paul
ISNI:       0000 0004 7969 442X
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2019
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Low-valent, low-coordinate or multiply bonded main group compounds are of interest for their reactivity. Properties usually observed for transition metals, such as small molecule activation, are possible for these classes of main group compounds. The development of the coordination chemistry of main group elements allows the synthesis of new types of species, which could not be achieved before, by providing electronic and kinetic stabilisation. In the following sections are presented reactivity studies of silylenes, low-valent silicon species, and phosphaborenes (RP=BR'), multiply bonded phosphorus-boron compounds. Chapter I gives an overview of low-valent and low-coordinate silicon chemistry. Two main types of silicon species can be distinguished in this area: silylenes and base-stabilised silicon compounds. Silylenes (:SiR2) are heavier analogue of carbenes (:CR2) and have simultaneously similar and different properties compared to carbenes. Although less studied than carbenes, silylenes also have interesting potential for coordination chemistry to transition metals or main group elements. Base-stabilised silicon compounds have been known for more than a century, however, only the recent use of N-heterocyclic carbene (NHC) ligands has allowed isolation of new low coordinate silicon species, such as the carbene-stabilised diatomic and triatomic silicon(0) clusters, which respectively feature two and three silicon atoms in the formal oxidation state of zero. Chapter II is a study of oxidative addition to an N-heterocyclic silylene 1,3-bis(diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene, a heavier analogue of N-heterocyclic carbene. An N-heterocyclic silylene was reacted with several main group halides (SiI4, PCl3 and BBr3). Oxidative addition was observed in each case, however, stability studies of the oxidative addition products show that only the product from the reaction with SiI4 is isolable. The reactivity of this product was studied toward reduction with alkali metals, reaction with bases, such as carbenes, organolithium reagents and phosphines. The addition of an excess of the N-heterocyclic silylene allows double oxidative addition from SiI4 to two N-heterocyclic silylenes. Finally, the addition of an excess of N-heterocyclic silylenes to BBr3 allows the observation of a relatively stable silylene-coordinated silylborane. Chapter III covers the attempted synthesis of a new type of N-heterocyclic silylene, which involves a bridgehead nitrogen atom, providing enhanced reactivity to this N-heterocyclic silylene compared to classical examples. This chapter includes the full synthesis and characterisation of the diamine ligand precursor N-1,3- diisopropylphenyl-3-piperidinemethanamine. The study of its reactivity was then carried out in order to insert silicon halide species into the structure, to reach the targeted N-heterocyclic silylene by reduction. The different conditions, which were tried on the ligand, did not successfully afford the targeted silane. The N-heterocyclic silylene could not be achieved. Chapter IV introduces the chemistry of mixed group III-V (13-15) compounds, which are widely used in electronic devices. Their synthesis involves harsh conditions such as chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE). Solution phase synthesis is a possible route to these mixed group III-V compounds, which will allow the use of milder conditions. Already achieved for some of them (GaAs, GaP, GaSb, InP, InSb), the solution phase synthesis of lighter mixed group III-V compounds, such as boron-phosphide (PB), is still elusive. The recent development of the chemistry of bas-estabilised phosphaborenes RP=BR'(L), mixed compounds involving a phosphorus-boron double bond, highlighted a possible way to make boron-phosphide through solution phase preparation. The use of N-heterocyclic carbenes (L) could also allow stabilisation of new allotropes of boron-phosphide PB(L). Chapter V explores the chemistry of minimally substituted base-stabilised phosphinoboranes [(Me3Si)2PBBr2(L)] (L = NHC) and phosphaborenes [Me3SiP=BBr(L)] achieved by base-promoted abstraction of trimethylsilyl halide from a phosphorus-borane adduct precursor [(Me3Si)3P→BBr3]. The functionalisation of [(Me3Si)2PBBr2(L)] affords the [H2PBBr2(L)] and similar base-promoted dehydrohalogenation allows the synthesis of the phosphaborene [HP=BBr(L)]. An unsaturated NHC used in this chemistry showed limited stability to the conditions used in the attempt to form base-stabilised boron-phosphide. The chemistry has been reexplored using a new NHC, which is expected to be more stable and enable the synthesis of base-stabilised boron-phosphide PB(L). The reactivity of phosphaborenes has been explored and hydrogenation of [HP=BBr(L)] or [(Me3Si)P=BBr](L) successfully gives the phosphinoboranes [H2PBHBr(L)] and [(Me3Si)HPBHBr(L)]. Base-promoted dehydrohalogenation from [H2PBHBr(L)] allows the observation of the base-stabilised parent diphosphadiboretane, [(HPBH)2(L)2].
Supervisor: Cowley, Michael ; Arnold, Polly Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: low valent silicon ; main group halide ; multiply bonded phosphorus-boron ; silylenes ; N-heterocyclic carbene ligands ; N-heterocyclic silylene