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

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ing does not allow for the possibility of an O-N bidentate coordination pocket like in V- 9 there are interesting potential oxidations states including the possibility of a zwitterion. This project has only been taken as far as the HCl salt (similar to the direct precursor for V-9) and while there has been some preliminary work put towards the formation of the dichloride salt not enough evidence has been collected to verify that this reaction has been completed successfully. The following will discuss the characterization data obtained for the dinitro species as well as the subsequent HCl salt. 5.4.2 Synthesis The first step of this reaction was originally carried out in an early attempt at obtaining V-11. After attempting to replicated the synthesis outlined in the original reference for this compound, 8 several other methods of nitration were attempted including the harsh conditions involving concentrated sulfuric acid as the solvent with the addition of concentrated nitric acid as the nitrating agent. When the 1,2-naphthoquinone was first dissolved in sulfuric acid at 0 °C the orange/brown solid gave way to a dark blue solution. Then a small amount of concentrated nitric acid, consistent with approximately 2 equivalents of NO 2 was added while the reaction mixture was held at 0 °C. This resulted in a slight red tinge emerging in the reaction mixture which was then warmed to room temperature and then further heated to approximately 60-70 °C for about 45 minutes. After this time the solution was clear and dark red and it was allowed to cool to room temperature. It was then poured on crushed ice resulting in a large amount of pale orange solid crashing out of the solution (V-15). This was filtered and washed with a small amount of water followed by diethyl ether to ensure that the compound would be 165
completely dry after being under vacuum for several hours. It was later discovered that when 1,2-naphthoquinone was reacted with concentrated sulfuric acid it resulted in both reduction to the diol as well as the formation of the carbon-carbon bond that was observed. 11 However the addition of the nitric acid both converted the diol back to the quinone and added a nitro group. Scheme 5-5. The reaction sequence of o-naphthoquinone to obtain V-15 and V-16. 166
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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
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(23) Rajca, A. Chem. Rev. 1994, 94,
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(53) Azuma, N.; Tsutsui, K.; Miura,
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(79) Decken, A.; Cameron, T. S.; Pa
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(102) Herz, R.; Leopold Cassella &
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(128) Aliaga-Alcalde, N., 2003. (12
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Chapter 2 - Structural and Magnetic
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2.2.2 pymDSDA Coordination Complexe
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2.2.3 DTDA Coordination Complexes o
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indicators tend to be very weak str
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In Figure 2-1a, the nickel complex
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2.2.3 Cyclic Voltametry The cyclic
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propensity for intermolecular Se-N
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dimerization motif. One possible ex
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the bridging ligand such that the D
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contacts into four different intera
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e acting as a closed-shell, S = 0,
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2.3.4 [Zn(hfac) 2 ] 2·pymDTDA (II-
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ancillary ligands and the nearly oc
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single molecular unit. Upon closer
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across the entire temperature regim
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2.5 Conclusions and Future Work It
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therefore chain formation. However
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The work presented in this chapter
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736(s), 723(s), 646(s), 632(s), 469
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(0.2023 g, 1.104 mmol) in 30 mL of
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(6) Chattoraj, S. C.; Cupka Jr, A.
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Chapter 3 - 5-oxo-5H-naphtho[1,2-d]
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triethylammonium chloride which was
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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
Page 187 and 188: good spectroscopic handle for this
Page 189 and 190: spectrum from about 1900 to 400 cm
Page 191 and 192: doublets of triplets associated wit
Page 193: adical, followed by the closed-shel
Page 197 and 198: changed substantially after the tra
Page 199 and 200: The reaction to produce V-15 was qu
Page 201 and 202: the proton two carbons away next to
Page 203 and 204: which is parallel to the mean plane
Page 205 and 206: of the 1,2,3-DTA rings could act as
Page 207 and 208: mixture was refluxed for 20 h yield
Page 209 and 210: the heat source was removed and the
Page 211 and 212: 1085(w), 1059(w), 1008(w), 917(w),
Page 213 and 214: ___________________________________
Page 215 and 216: Crystallography P 2 1 /c a = 9.1678
Page 217 and 218: Compound Name: 4-(2′-pyrimidyl)-1
Page 219 and 220: Compound Name: [μ-4-(2′-pyrimidy
Page 221 and 222: Magnetometry 192
Page 223 and 224: Crystallography P-1 a = 8.9576, b =
Page 225 and 226: Compound Name: [μ-4-(2′-pyrimidy
Page 227 and 228: Magnetometry: 198
Page 229 and 230: Crystallography: P2 1 /n a = 19.884
Page 231 and 232: Compound Name: 5-oxo-5H-naphtho[1,2
Page 233 and 234: 204
Page 235 and 236: 206
Page 237 and 238: MS (EI + ): 208
Page 239 and 240: Compound Name: 5-chloro-1H-[1,2,5]t
Page 241 and 242: Compound Name: 3-nitro-1,2-naphthaq
Page 243 and 244: 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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222
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1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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