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Title: Studies on some pentachlorophenyl-containing compounds.
Authors: Rimmer, Gerald David.
Award date: 1971
Presented at: University of Leicester
Abstract: The first section of this work reviews the organic chemistry of pentachlorophenyl derivatives and describes the preparation of the compound (C6CI5)n Sn Ph(4-n) where (n = 1, 2 or 4) and C6Cl5HgX (X = C6Cl5 , Cl and Br). Mossbauer spectroscopic data for the tin compounds are presented, and the respective isomer shift and quadrupole splitting data are discussed in terms of an imbalance in the polarity of the tin-ligand a-bonds. Measurements of (Hg - X) for C6Cl5HgX (X = Cl and Br) are consistent with these findings. N, Q, R, studies on the mercury compounds are interpreted in terms of interaction between o-chlorine atoms on the aromatic rings and mercury, A thermogravimetric analysis of Bu2 nSn(C6Cl5)2 infers a similar interaction in this compound. Evidence for two new pentachlorophenoxy-derivatives of titanium, (C6Cl50)4Ti and (C6Cl5O)2 TiCl2 is also cited. The preparations of (C6Cl5 )n P Ph(3-n) and C6Cl5AsPh2 and the complexes SnCl4 Pcl2, [Pt Pcl2 x2] (X = Cl, Br), [Rh(CO)Pcl 2CI] and [Rh Pcl2 Cl]2 are reported. The failure of the latter to form carbonyl derivatives is noted and tentatively attributed to interaction between o-chlorine atoms and Rh, Ligand displacement ractions are also reported for these compounds. The ability of the C6Cl5S group to act as a pseudo halogen is described in the preparation of M(SC6Cl5) (M = Tl, Ag, Ni and Ph3Sn); [Rh(CO )2 SC6Cl5 ]2 (diene Rh SC6Cl5 ]2 (diene = cycloocta 1,5,diene, norbornadiene, and dicyclo- pentadiene ) and [C6Cl5 S.Fe (CO )2rr-Cp]. The infra-red spectra of the carbonyl derivatives are discussed in terms of the electron Withdrawing ability of the C6Cl5S group and related to the failure of (PhO)3P to cleave the C6Cl5S bridge in the diene complexes. The preparation of [COD.Rh.SC6F2]2 is also reported. The mass spectra and tentative fragmentation schemes for (C6F5)3M (M = As and Sb), (2,6 C6F2H3)3M (M = P and As),(2,5 C6F3H3)3P, C6Cl5HgX (X =C6 Cl5, Cl, Br), Bun2Sn(C6Cl5 )2, (C6Cl5)Np ph(3-n) (C6Cl5) As Ph2 are reported and discussed. Comparisons are drawn between the Gp.V C6Cl5 and C6F6 derivatives and for the Sn and Hg compounds, modes of fragmentation are related, to the properties of the previously described derivatives.
Level: Doctoral
Qualification: Ph.D.
Rights: Copyright © the author. All rights reserved.
Appears in Collections:Theses, Dept. of Chemistry
Leicester Theses

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