Browsing Ph.D. Chemistry by Subject "Gallium, main group, low valent"
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Reactivity of a Low Valent Gallium CompoundThe work described in this thesis is conducted to expand the reactivity of the β-diketiminate gallium(I) compound, NacNacGa (NacNac=[ArNC(Me)HC(Me)NAr]−, Ar=2,6-iPr2C6H3). The reactivity of NacNacGa towards various unsaturated compounds is studied. In particular, reaction between NacNacGa and phenyl isothiocyanate resulted in the oxidative addition of the C=S bond under ambient conditions, leading to the isolation cyclization product NacNacGa(κ2-S2CNPh) and sulfide isocyanide-bridged dimer (NacNacGa)2(μ-S)(μ-CNPh). Additionally, a [1+4] cycloaddition with a conjugated aldehyde (methacrolein) and a [1+2+3] cycloaddition with isocyanate and carbodiimide are presented. The oxidative cleavage of P=S bond of triphenylphosphine sulfide at increased temperatures gave the previously reported sulfide bridged gallium dimer. In situ oxidation of NacNacGa in the presence of substrates featuring donor sites led to the C-H activation reactions. As such, C-activation of pyridine N-oxide, pyridine, cyclohexanone, DMSO, and Et3P=O by a transient NacNacGa=O resulting in the corresponding gallium hydroxides is demonstrated. DFT calculations suggested initial formation of adducts between substrates and NacNacGa=O followed by a C-H bond abstraction from the substrate. Similarly, a transient gallium imide NacNacGa=NSiMe3, generated from the reaction of NacNacGa with trimethylsilyl azide, is shown to cleave C-H bonds of pyridine, cyclohexanone, ethyl acetate, DMSO, and Et3P=O with the formation of gallium amides. In an attempt to isolate a gallium alkylidene, NacNacGa was treated with trimethylsilyl(diazomethane). Instead, a monomeric gallium nitrilimine and a metalated diazomethane were obtained. The gallium nitrilimine undergoes 1,3-addition reaction with phenylsilane and catecholborane forming gallium hydrazonides. Its reaction with diborane resulted in the formal nitrene insertion into the B-B bond to produce a gallium diborylamide. DFT calculations revealed intermediate gallium alkylidene formation from the reaction of NacNacGa with diazomethane that upon reaction with the second equivalent of diazomethane leads to a gallium nitrilimine.