The solvolysis of methyltin(IV) chlorine compounds of the general type (CH₃)nSnCl₄₋n with n ranging from 0 to 4, is studied in aqueous and anhydrous hydrogen fluoride under a variety of conditions. The studies in anhydrous HF have resulted in the synthesis of the new compounds methyltin(IV) trifluoride, dimethyltin(IV) chloride fluoride and methyltin(IV) dichloride fluoride. Methyltin(IV) chloro difluoride could not be synthesized in this way. A special monel reflux reactor was utilized for these reactions. Attempts to solvolyze vinyl- and phenyltin compounds with anhydrous HF did not yield pure products. In these cases, the evidence indicates that cleavage of the Sn-Cl and Sn-C bonds occurs in an unpredictable manner. A convenient method for the preparation of SnCl₂F₂ is found in the solvolysis of SnCl₄ with anhydrous HF. Interaction of this compound with either S₂O₆F₂ or C1OSO₂F results in the formation of SnF₂(SO₃F)₂. Attempts to find alternative synthetic routes to SnF₂(SO₃F)₂ were unsuccessful. Structural proposals for these compounds are based on infrared, Raman and ¹¹⁹Sn Mössbauer spectra. All the new compounds are found to be polymeric via fluorine or fluorosulphate bridges, resulting in penta- or hexacoordination around tin. Dialkyltin(IV) difluorides are easily obtained when the corresponding chlorides are solvolyzed in aqueous hydrogen fluoride. Dimethyltin, diethyltin, dipropyltin, dibutyltin and dioctyltin difluorides are prepared in this way. However, divinyltin(IV) difluoride and diphenyltin(IV) difluoride cannot be made via this route. Also, CH₃SnF₃ and the methyltin(IV) chloride fluorides cannot be synthesized from solvolysis reactions involving aqueous HF. / Science, Faculty of / Chemistry, Department of / Graduate

Thesis (Ph. D.)--University of Texas at Austin, 2002. / Vita. Includes bibliographical references. Available also from UMI Company.

Thesis (Ph. D.)--University of Texas at Austin, 2002. / Vita. Includes bibliographical references. Available also from UMI Company.

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The single crystal X-ray analyses of KSO(3)F and NH(4)SO(3)F are reported. Both are orthorhombic (space group: Pnma) with cell dimensions a =8.62 Å, b =5.84, c = 7.35 and a = 8.97 Å, b = 5.99, c = 7.54 respectively. Two of the anion ligand positions are completely disordered in KSO(3)F (i.e. SO(2)X(2)¯, X = 50% F and 50% O). A hydrogen bond between NH(4)+ and one of the SO(3)F ¯ disordered positions causes that ligand position to be occupied preferentially by oxygen in NH(4)SO(3)F. The laser Raman spectrum of CH(3)C(OH)(2)SO(3)F is determined. The vibrational spectra and SO(3)F¯ dimensions are compared in NK(4)SO(3)Fr KSO(3)F, CH(3)C(OH)(2)SO(3)F, and (CH3)2 Sn(SO3F)2. The SO(3)F¯ dimensions are surprisingly constant with only S-F in (CF3)2Sn(SO3F)2 (in which there is greatest X-OSO(2)F interaction) shorter than in the others. vS-F increases with increasing cation-anion interaction. The vibrational spectra of the fluorosulfates of Li+, Na+ , K+, NH4+, Rb+, Cs+, (CH3)4N+, and (C6H5)4As+ are reported. vS-F increases 108 cm(-1) with polarizing power of the cation (from (C6H5)4As+ to Li+) and vS-O (average) increases in the same series by 35 cm(-1). The preparation and conductivity in HSO(3)F of Sn(SO3F)2 and Pb(SO3F)2 are reported. Both are weaker bases than Ca(SO3F)2. The Mössbauer parameters of Sn(SO3F)2 (ὁ= +4.17 mm/sec, ∆ = 0.73 mm/sec) indicate it is one of the most ionic SnII compounds yet reported. A new preparative route for obtaining M(SO3F)2 {M(OOCC6H5)2 + HSO3F} is reported. The vibrational spectra of the bis-fluorosulfates of Mg(II), Ca(II), Sr(II), Ba(II), Sn(Il), Pb(II), Cu(II), Zn(II), Cd(II), Mn(II), and Hg(II) are reported. vS-O (average) and vS-F cannot be correlated with polarizing power of the cation or M2+ ionization potential but are in all cases higher than for the mono-fluorosulfates. The differences among the spectra are explained in terms of polarizing power of the cation, some multiple bonding to fluorine and different site-symmetries for the SO3 F¯ anion. / Science, Faculty of / Chemistry, Department of / Graduate

Reactions of different alcohols with 2-hydroxy - 1- trifluoromethyl -1,2,2-trifluoroethanesulfonic acid sultone were studied. Six new esters were prepared: C6F5OC(O)CF(CF3)SO2F, CH3CH2OC(O)CF(CF3)SO2F, CF3CH2OC(O)CF(CF3)SO2F, (CF3)2CHOC(O)CF(CF3)SO2F, CH2=CHCH20C(O)CF(CF3)SO2F, (CH2OC(O)CF(CF3)SO2F)2. Analytical data, infrared, nmr and mass spectra are presented supporting the proposed structures for these new compounds.

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Thesis (Ph.D.) -- McMaster University, 2003. / Includes bibliographical references (leaves 152-168). Also available via World Wide Web.