1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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(17) Davies, J. E.; Less, R. J.; May, I.; Rawson, J. M. New J. Chem. 1998, 763. (18) Fatila, E. M.; Goodreid, J.; Clérac, R.; Jennings, M.; Assoud, J.; Preuss, K. E. Chem. Commun. 2010, 46, 6569. (19) Wu, J. Ph.D. Dissertation, University of Guelph, 2008. (20) Banister, A. J.; Bricklebank, N.; Clegg, W.; Elsegood, M. R. J.; Gregory, C. I.; Lavender, I.; Rawson, J. M.; Tanner, B. K. Chem. Commun. 1995, 679. (21) Hearns, N. G. R.; Clérac, R.; Jennings, M.; Preuss, K. E. Dalton Trans. 2009, 3193. (22) Bryan, C. D.; Cordes, A. W.; Haddon, R. C.; Hicks, R. G.; Oakley, R. T.; Palstra, T. T. M.; Perel, A. J. Chem. Commun. 1994, 1447. (23) Bryan, C. D.; Cordes, A. W.; Goddard, J. D.; Haddon, R. C.; Hicks, R. G.; MacKinnon, C. D.; Mawhinney, R. C.; Oakley, R. T.; Palstra, T. T. M.; Perel, A. S. J. Am. Chem. Soc. 1996, 118, 330. (24) Yost, D. M.; Kircher, C. E. J. Am. Chem. Soc. 1930, 52, 4680. 107
Chapter 3 - 5-oxo-5H-naphtho[1,2-d][1,2,3]dithiazol-4-yl acetate. 3.1 General The compound 4-hydroxy-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one (III-1), 1 was originally discovered accidently while trying to isolate the neutral radical 4,5-dionenaphtho[1,2-d][1,2,3]dithiazolyl (III-2). 1 It was found that III-2 was sensitive to the presence of water and can give rise to the hydroxyl derivative III-1. Several attempts were made to coordinate the neutral radical III-2 to a metal center using a variety of metal containing starting materials; however it was postulated that lack of charge and adequate donor properties resulted in the coordination being unfavourable. 1 It is possible to reduce III-2 to a closed-shell anion, which can be isolated as the lithium salt which was characterized via X-ray crystallography as both a hydrate and an anhydrous compound. 1 It was discovered that with a negative charge the O-O chelation pocket possessed strong enough donor properties to form coordination complexes with several metal ions. However for the antimony complex only the oxygen atom which possessed the majority of the negative charge is within the covalent radius of the metal ion [2.065(3) Å]. The second metal oxygen bond was much longer, and while outside of the covalent radius, was within the van der Waals radii of the metal and oxygen atoms [2.457(4) Å]. This can likely be attributed to the poor donor properties associated with the doubly bonded oxygen atom and provides some insight into why coordination of the neutral radical was unsuccessful. 1 These and related compounds were extensively explored and it was discovered by cyclic voltametry that the radical III-2 shows a chemically reversible reduction to the closed-shell anion, but a second reduction to the open shell dianion was not shown to be 108
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1,2,3-Dithiazolyl and 1,2,35-Dithia
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an individual binuclear coordinatio
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weren’t sure about something our
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2.1 General........................
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5.3 Reverse oDTANQ.................
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LIST OF FIGURES AND SCHEMES Figure
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Figure 2-12. Magnetic susceptibilit
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GLOSSARY OF ABBREVIATIONS ° Degree
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K k k B LMCT ls LUMO Kelvin Exchang
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LIST OF STRUCTURES I-1 I-2 I-3 I-4
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I-16a I-16b I-16c I-16d I-16e I-16f
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I-22 I-23 I-24 I-25 exo I-26 endo x
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I-34 I-35 II-3 II-4 II-1 xxv
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III-2 III-1 III-3 III-4 III-5 III-6
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V-7 V-8 V-9 V-10 V-11 V-12 V-13 V-1
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Chapter 1 - General Introduction 1.
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linear relationship shown in Figure
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A plot of χT vs. T is an important
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examination of phenyl methylene. In
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different atomic nuclei. Qualitativ
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3) 14 and a variety of thiazyl base
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with one another with an energy bar
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magnetic properties and undergoes a
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heteroatoms which could facilitate
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Figure 1-5. Qualitative molecular o
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temperature. 64 This was a very imp
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dimerization and therefore a quench
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e enough to overcome the energetica
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eaches the lower end of the investi
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DTDAs has been to exploit the rearr
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1.3.4 1,2,3-Dithiazolyl Radicals (I
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aromatic ring not only protects the
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is quite similar to the spin-polari
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compound there are many competing m
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a b c d e Figure 1-16. a) Nonorthog
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would result in non-orthogonal over
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platinum center as well as the phos
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substantial amount of unpaired elec
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I-28 I-29 I-30 The metals manganese
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gave a combination of 2 mononuclear
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changes related to geometric, chemi
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Finally, the last chapter reviews t
Page 85 and 86: (23) Rajca, A. Chem. Rev. 1994, 94,
Page 87 and 88: (53) Azuma, N.; Tsutsui, K.; Miura,
Page 89 and 90: (79) Decken, A.; Cameron, T. S.; Pa
Page 91 and 92: (102) Herz, R.; Leopold Cassella &
Page 93 and 94: (128) Aliaga-Alcalde, N., 2003. (12
Page 95 and 96: Chapter 2 - Structural and Magnetic
Page 97 and 98: 2.2.2 pymDSDA Coordination Complexe
Page 99 and 100: 2.2.3 DTDA Coordination Complexes o
Page 101 and 102: indicators tend to be very weak str
Page 103 and 104: In Figure 2-1a, the nickel complex
Page 105 and 106: 2.2.3 Cyclic Voltametry The cyclic
Page 107 and 108: propensity for intermolecular Se-N
Page 109 and 110: dimerization motif. One possible ex
Page 111 and 112: the bridging ligand such that the D
Page 113 and 114: contacts into four different intera
Page 115 and 116: e acting as a closed-shell, S = 0,
Page 117 and 118: 2.3.4 [Zn(hfac) 2 ] 2·pymDTDA (II-
Page 119 and 120: ancillary ligands and the nearly oc
Page 121 and 122: single molecular unit. Upon closer
Page 123 and 124: across the entire temperature regim
Page 125 and 126: 2.5 Conclusions and Future Work It
Page 127 and 128: therefore chain formation. However
Page 129 and 130: The work presented in this chapter
Page 131 and 132: 736(s), 723(s), 646(s), 632(s), 469
Page 133 and 134: (0.2023 g, 1.104 mmol) in 30 mL of
Page 135: (6) Chattoraj, S. C.; Cupka Jr, A.
Page 139 and 140: triethylammonium chloride which was
Page 141 and 142: 3.3.2 Mass Spectrometry A sample of
Page 143 and 144: 3.3.4 X-ray Crystallography Crystal
Page 145 and 146: a 2-fold screw axis across half of
Page 147 and 148: number of electrons that this compo
Page 149 and 150: often generated in situ although wa
Page 151 and 152: similar to compounds II-1 and II-2,
Page 153 and 154: 3.6 Experimental General All reacti
Page 155 and 156: Chapter 4 - The Polymorphism of Tri
Page 157 and 158: 4.3 Discussion Prior to the discove
Page 159 and 160: (derived from angles ranging from 4
Page 161 and 162: a b c Figure 4-2. Packing diagrams
Page 163 and 164: polymorphs observed and are therefo
Page 165 and 166: Chapter 5 5.1 Overview There are se
Page 167 and 168: success and so a Herz ring closure
Page 169 and 170: did not immediately precipitate, bu
Page 171 and 172: Figure 5-2 shows the IR spectra for
Page 173 and 174: comparison of the infrared data obt
Page 175 and 176: discussed in section 5.2.2. As the
Page 177 and 178: ing was formed. One of the nitrogen
Page 179 and 180: equired to obtain a decent agreemen
Page 181 and 182: Considerations have been put toward
Page 183 and 184: chelation pocket is similar to that
Page 185 and 186: the mixture was filtered to remove
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good spectroscopic handle for this
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spectrum from about 1900 to 400 cm
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doublets of triplets associated wit
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adical, followed by the closed-shel
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completely dry after being under va
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changed substantially after the tra
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The reaction to produce V-15 was qu
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the proton two carbons away next to
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which is parallel to the mean plane
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of the 1,2,3-DTA rings could act as
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mixture was refluxed for 20 h yield
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the heat source was removed and the
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1085(w), 1059(w), 1008(w), 917(w),
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___________________________________
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Crystallography P 2 1 /c a = 9.1678
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Compound Name: 4-(2′-pyrimidyl)-1
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Compound Name: [μ-4-(2′-pyrimidy
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Magnetometry 192
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Crystallography P-1 a = 8.9576, b =
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Compound Name: [μ-4-(2′-pyrimidy
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Magnetometry: 198
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Crystallography: P2 1 /n a = 19.884
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Compound Name: 5-oxo-5H-naphtho[1,2
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204
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206
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MS (EI + ): 208
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Compound Name: 5-chloro-1H-[1,2,5]t
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Compound Name: 3-nitro-1,2-naphthaq
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Compound Name: 3,4-dioxo-3,4-dihydr
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Compound Name: 4,5-dioxo-4,5-dihydr
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Compound Name: 6,6′-dinitro-1,1
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220
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1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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