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

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The other piece of information acquired for the compounds shown in scheme 5-4 was the 1 H NMR. Compound V-11 has five protons and each has a unique environment, resulting in five signals in the 1 H NMR spectrum each integrated to only one proton. The signal furthest downfield is seen at 8.67 ppm and is a singlet. This signal corresponds to the hydrogen atom in the 4 position on the ring which is otherwise fully substituted and Figure 5-14. 1 H NMR spectrum of V-13 at 300 MHz in d 6 -DMSO. so there are no other protons nearby for it to couple with. As the four protons on the other ring are all adjacent and therefore each of the signals exhibit coupling which can be described as multiplets, but have discrete coupling constants consistent with the multiplicities given in the experimental section and discussed here. There are two 161
doublets of triplets associated with the two protons in the 6 and 7 positions and two doublets of doublets associated with the protons in the 5 and 8 positions. Compound V-12 had poor solubility in organic media and DMSO which had been used for the other compounds, resulted in partial deprotonation of the hydrochloride salt giving two distinct species in the spectrum. Therefore the 1 H NMR spectrum for this compound is not be included. The 1 H NMR spectrum for V-13 is shown in Figure 5-14. The coupling patterns for these signals are identical to those seen in the spectrum for V-11, although the shifts have changed and are no longer overlapping. While their relative positions are the same, they have all shifted upfield as the electropositive sulfur atoms in the 1,2,3-DTA ring are not as electron withdrawing as the nitro group from V-11. The actual values for the 1 H NMR shifts are given in the experimental sections. 5.3.5 Conclusions and Future Work As a structural isomer of III-2 and V-10, the radical V-9 is a natural extension of the work which has been put toward 1,2,3-DTA radicals with quinone moieties by our group in the last few years. Investigations into III-2 have revealed several limitations which V- 9 may not have. While attempts at coordination of the neutral radical III-2 failed, it has been demonstrated that having a nitrogen atom ortho to the one of the quinone oxygen atoms does provide a suitable coordination environment for nickel(II) with ancillary hfac ligands by successful coordination of V-10 and methylated derivatives. 10 It is therefore quite possible that coordination complexes such as V-14 may be possible. As 162
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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]
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
Page 187 and 188: good spectroscopic handle for this
Page 189: spectrum from about 1900 to 400 cm
Page 193 and 194: adical, followed by the closed-shel
Page 195 and 196: completely dry after being under va
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
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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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