A solution and solid state study of niobium complexes University of ...

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Chapter 5 Figure 5.6: Photo-Multiplier data of [NbCl2(OMe)3(MeOH)] (5 x 10 -5 M) and [acacH] (5 x 10 -4 M) in MeOH fitted to (a) a one-step pseudo first-order reaction model and (b) a two- consecutive-step pseudo first-order mathematical model at 35.0 °C and λ = 330nm. It is clear from Figure 5.6 that the data fits the first model better, indicating a one-step pseudo first-order reaction. Preliminary experiments indicated that plots of kobs vs [acacH] for the reactions observed on the stopped-flow apparatus yield straight lines, whereas similar plots for the slower, second reaction yield non-linear results. 87 (a) (b)
5.3.3 Derivation of the rate law Chapter 5 The following rate law can be derived from Scheme 5.1: ( M-acac) d Rate= =k 2 M-acacH -k -2 M-acac dt The definition of K1 yields the following equation: [ ] [ ] [ M-acacH] [ ][ ] 88 (5.3) K 1 = (5.4) M acacH The total niobium species at any time in solution, Mtot, is defined by: M tot = [ M ] + [ M-acacH] (5.5) By substituting (5.4) in (5.5) the following equation is obtained: [ M-acacH] [ ] [ ] M tot = + M-acacH K 1 acacH ⎛ 1 ⎞ = ⎜ +1⎟ M-acacH ⎜ K 1[ acacH] ⎟ ⎝ ⎠ 1[ ] [ ] [ ] ⎛1+K acacH ⎞ = ⎜ ⎟ M-acacH ⎜ K 1 acacH ⎟ ⎝ ⎠ [ ] Substitution of (5.6) in (5.3) yields: [ ] [ ] [ ] M tot .K 1 . acacH M-acacH = 1+K 1 acacH tot [ ] [ ] k .K . ⎡ 2 1 M acacH Rate= ⎣ ⎤ ⎦ -k -2 M-acac 1+K 1 acacH [ ] (5.6) (5.7)
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A solution and solid state study of
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Table of contents Abbreviations and
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3.4 Infrared Spectroscopy (IR) ....
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Abbreviations and Symbols Abbreviat
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Abstract 93 Nb NMR was successfully
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Opsomming 93 Nb KMR is met sukses g
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Chapter 1 metals. 3 Due to Wollasto
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Synopsis... 2. Literature Review of
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Chapter 2 Niobium resembles tantalu
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2.1.2 Uses Chapter 2 Niobium has a
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2.2 Separation of Nb and Ta 2.2.1 M
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Chapter 2 Buachuang et al. 16 repor
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Chapter 2 Niobium oxide surfaces ex
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2.4.6 Water absorption Chapter 2 Th
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Chapter 2 been reported in literatu
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Chapter 2 containing niobium as the
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Chapter 2 conclusions, with regard
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Chapter 2 Figure 2.5: Structure of
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2.6.3.3 [NbCl3O(ttbd) - ] Chapter 2
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Chapter 2 (a) (b) Figure 2.10: Stru
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2.7 Alkoxides Chapter 2 Specific kn
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Chapter 2 Reactions of dialkylamid
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Chapter 2 other NbCl5-x(OMe)x produ
Page 47 and 48: Chapter 2 In 1991 Lee et al. 83 pub
Page 49 and 50: EtO EtO EtO EtO Cl Nb Cl Cl Nb Cl R
Page 51 and 52: Chapter 2 The hemicarbonate formed
Page 53 and 54: Synopsis... 3. Synthesis and Charac
Page 55 and 56: Chapter 3 with γ = magnetogyric ra
Page 57 and 58: Chapter 3 electromagnetic spectrum
Page 59 and 60: 3.5.1 Bragg’s law Chapter 3 Bragg
Page 61 and 62: 3.5.3 ‘Phase problem’ Chapter 3
Page 63 and 64: Chapter 3 A = ∑ ε cl (3.14) In
Page 65 and 66: Chapter 3 t1/2 = 54 = . 3.7 Sy
Page 67 and 68: 3.7.2.4 Synthesis of [NbCl4(acac)]:
Page 69 and 70: 4. Crystallographic Synopsis... Cha
Page 71 and 72: Chapter 4 packages 2 respectively.
Page 73 and 74: Chapter 4 4.3 Crystal Structure of
Page 75 and 76: Chapter 4 longer bonds (C1-C2, C2-C
Page 77 and 78: Chapter 4 Figure 4.5: Packing of [N
Page 79 and 80: Chapter 4 Figure 4.7: Molecular str
Page 81 and 82: Chapter 4 Table 4.5: Selected bond
Page 83 and 84: Chapter 4 Figure 4.11: Molecular st
Page 85 and 86: Chapter 4 Figure 4.12: The phacac p
Page 87 and 88: Chapter 4 Table 4.9: Hydrogen bonds
Page 89 and 90: Chapter 4 According to our knowledg
Page 91 and 92: 5.2 Experimental procedures 5.2.1 K
Page 93 and 94: Chapter 5 corresponds to one specie
Page 95 and 96: 5.3 Results and Discussion 5.3.1 Pr
Page 97: Chapter 5 Figure 5.5: Typical UV/Vi
Page 101 and 102: Chapter 5 The Stopped-flow data (fa
Page 103 and 104: Chapter 5 Figure 5.9: Eyring plot,
Page 105 and 106: Chapter 5 However, more information
Page 107 and 108: Chapter 6 second reaction entailed
Page 109 and 110: Appendix A Table 1.3: Bond angles (
Page 111 and 112: Appendix A A 2 Supplementary Data f
Page 113 and 114: Appendix A C(16)-H(16B) 0.96 C(16)-
Page 115 and 116: Appendix A O(7)-C(10)-C(11) 123.6 (
Page 117 and 118: Appendix A H(18E)-C(18B)-H(18F) 109
Page 119 and 120: Appendix A H(18F) 6243 6605 575 75
Page 121 and 122: Appendix A Table 3.3: Bond angles (
Page 123 and 124: Appendix A Table 3.4: Anisotropic d
Page 125: Appendix B Appendix B B 1 Supplemen
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A solution and solid state study of niobium complexes University of ...

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