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Title: Coordination chemistry of pendant aniline aza-macrocycles
Author: Tatchell, Thomas
ISNI:       0000 0004 2748 2898
Awarding Body: Cardiff University
Current Institution: Cardiff University
Date of Award: 2005
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The selective functionalisation of triazamacrocycles is investigated herein, with the focus on 1, 4, 7-triazacyclononane (tacn) The ligands tris (5-fluoro, 2- aminophenyl) 1, 4, 7-triazacyclononane (L1), tris (4-fluoro, 2-aminophenyl) 1,4, 7- triazacyclononane (L") and tris (3-fluoro, 2-ammophenyl) 1, 4, 7-triazacyclononane (L ) were studied. X-Ray crystal data was obtained for (L,)M (C104)2.x:MeCN where M=Mn,,/FeII/Ni"/CuII/Znn/CdII/Hgn, (L2)M (C104)2 xMeCN where M=Mn1I/Fe,I/NiII/CuII/ZnII/Cdn and (L3)M (C104)2 xMeCN where M=Mn,1/NiI,/Cun/Zn,I/Cd,,/Pb11 complexes. The (L,)Cu (C104)2 complex exhibits a rare dynamic Jahn-Teller effect in the solid state. Selected compounds exhibit an interesting capping mode by their perchlorate counterions, with threefold-hydrogen bonding through the oxygen to the amine protons. The (L3)Pb (C104)2 crystal structure exhibits a typical geometry which accommodates a stereoactive lone pair from the lead centre. The variable temperature 'H NMR of tris 1, 4, 7-(2- aminophenyl) 1, 4, 7-triazacyclononane zinc bis tetraphenylborate was carried out over 298K-193K and spectra are included within. All complexes characterized by 'H NMR, 13C NMR, 19F NMR, IR, UV and where appropriate Mossbauer spectroscopy. The investigation into the synthesis and chemistry of the novel sulphonamide pentaazamacrocycles 1 -(/-tolylsulphonyl), bis 4, 7-(2-aminophenyl) - 1, 4, 7-triazacyclononane (L4), l-(/7-methoxyphenylsulphonyl), bis 4, 7-(2- aminophenyl) -1,4, 7-triazacyclononane (L5), l-(p-fluorophenylsulphonyl), bis 4, 7-(2-aminophenyl) -1,4, 7-triazacyclononane (L6) and 1-(2-mesitylsulphonyl) bis 4, 7-(2-aminophenyl) 1, 4, 7- tnazacyclononane (L7). The complexation with differing transition metals afforded the relevant complexes and X-Ray data was obtained for (L4)Ni/Zn/Cd.MeCN (C104)2.MeCN, (L4)Pb(C104) (C104).2(MeCN), 2 (L4)Cu (C104)4,4MeCN MeOH, (L5)Ni/Zn MeCN (C104)2.MeCN, and (L6)Ni MeCN (C104)2 MeCN H20. The (L4)Zn/Hg/Pb.MeCN (C104)2 MeCN, (L5)Zn/Hg MeCN (C104)2.MeCN, (L6)Zn MeCN (C104)2 MeCN and (L7)Zn MeCN (C104)2 MeCN compounds exhibit an unusual amine pattern in the 'H NMR. This was further studied by variable temperature *H NMR over the range of 298K-418K. The (L4)Cu(C104)2 crystal structure shows two complexes of the same compounds crystallizing in the same cell, each with slightly differing dimensions, but both of square based pyramidal geometry. The (L4)Pb(C104) C104.2.MeCN crystal structure exhibits a typical geometry which accommodates a stereoactive lone pair from the lead centre The bis sulphonamide l-(2-aminophenyl)-bis 4, 7-(/xira-tolylsulphonyl) 1, 4, 7- triazacyclononane (L8) was also prepared and its complexation of L8Ni/Cu/Zn/Cd coordination chemistry expanded. The fluorinated 7V-aryl tacn class was expanded by producing bis and tris ortho meta para-fluorinated phenyl ligands. This selective methodology led to the development of a tri substituted tacn ring with meta and /wra-fluorinated aromatic rings. We report the electronic spectroscopic examination of the autocatalytic oxidative degradation of the macrocyclic aniline moiety over 120hrs. The synthesis of mono l-(5-fluoro, 2-aminophenyl) bis 4, 7, (2-aminophenyl) 1, 4, 7- tnazacyclononane (L9), and mono l-(4-fluoro, 2-aminophenyl) bis 4, 7, (2- aminophenyl) 1, 4, 7-triazacyclononane (L10) are reported. The X-Ray single crystal data was collected for (L9)Mn/Zn (C104)2 The synthesis of 1, 4-bis-(2-amino, 4-fluorophenyl) homopiperizene (Ln) and its X-Ray crystal structure of (LnNi 2 MeCN)(C104)2 is described The conversion of N, N' bis (2-aminophenyl) 1, 4-diazacycloheptane by reaction with p- toluenesulphonyl chloride afforded N, AT bis (2-tosylaminophenyl) 1, 4- diazacycloheptane (Lu). Reaction with nickel perchlorate afforded the neutral complex (L')Ni . This dianionic ligand is proposed as a porphyrin analogue.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available