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Title:Synthetic studies of sodium aminodiboranate salts with electronwithdrawing substituents
Author(s):Daly, Connor I.
Advisor(s):Girolami, Gregory
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:M.S.
Genre:Thesis
Subject(s):Sodium Aminodiboranates
Electron-Withdrawing Substituents
Abstract:Magnesium diboride, MgB2, has the highest superconducting critical temperature of all traditional superconductors and is being considered for the fabrication of superconducting integrated circuits that can operate at higher temperatures than analogous niobium alloy circuits. A significant barrier to preparing superconducting MgB2 thin films, however, is that the films must be deposited below 300 C to prevent Mg from subliming out of the film and causing loss of the superconducting properties. One approach to solve this problem is to prepare low-temperature chemical vapor deposition (CVD) precursors which would enable deposition of MgB2 at temperatures low enough to prevent loss of Mg from the thin film. In chapter 1, we describe the synthesis of three new sodium aminodiboranate salts, Na(BH3)2NRR′, with trimethylsilyl groups on nitrogen. These compounds – sodium N,N-bis-(trimethylsilyl)¬aminodiboranate, sodium N-trimethylsilylamino¬diboranate, and sodium N-methyl-N-trimethylsilylaminodiboranate – were prepared by the reaction of μ-aminodiborane(6) species with sodium hydride. IR, 1H NMR, 13C NMR, and 11B NMR spectra are reported for all of these compounds, along with the crystal structures of N-trimethylsilyl¬amino¬diboranate and N-methyl-N-trimethylsilylaminodiboranate. Comparisons of 11B NMR chemical shifts suggest that steric, inductive, and hyperconjugative effects of the substituents on nitrogen are all in competition in these systems. In chapter 2 we describe the preparation of fluorinated aminodiborantes, although here the longer reaction times required for their synthesis lead to undesirable production of butoxyborate species through the ring-opening reaction of thf with BH3. To circumvent this problem, we employed non-cyclic ethers such as diglyme and cyclopentyl(methyl)ether to investigate the preparation of μ-aminodiborane(6) species from the fluorinated amines N,N-bis(2,2,2-trifluoroethyl)¬amine, N-(2,2,2-trifluoroethyl)amine, and N-methyl-N-(2,2,2-trifluoro¬ethyl)¬amine. We find that there is a correlation between the pKa of the ammonium form of the amine with the relative stabilities of the μ-aminodiborane(6) and aminoborane: N,N-bis(2,2,2-trifluoroethyl)amine forms the aminoborane preferentially, whereas both N-(2,2,2-trifluoroethyl)amine and N-methyl-N-(2,2,2-trifluoroethyl)¬amine form the -aminodiborane(6) in good yields. Sodium N-methyl-N-(2,2,2-trifluoroethyl)¬aminodiboranate was prepared and characterized by 11B NMR spectroscopy, although efforts to isolate it were unsuccessful.
Issue Date:2020-05-15
Type:Thesis
URI:http://hdl.handle.net/2142/108071
Rights Information:Copyright 2020 Connor Daly
Date Available in IDEALS:2020-08-26
Date Deposited:2020-05


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