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half-integer in value. This class is possible when the ligand environment is similar or identical for each of the two metal sites in the complex. In fact, Robson type dianionic tetraimino-diphenolate ligands which provide equivalent N2O2 environments for two metal centres have stabilized the mixed valence diiron complexes of class III. The bridging ligand needs to be very good at electron transfer, be highly conjugated, and be easily reduced.
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136:(IT or IVCT) band, a broad intense absorption in the infrared or visible part of the spectrum, and also exhibit magnetic exchange coupling at low temperatures. The degree of interaction between the metal sites can be estimated from the absorption profile of the IVCT band and the spacing between the sites. This type of complex is common when metals are in different ligand fields. For example,
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Class III, wherein mixed valence is not distinguishable by spectroscopic methods as the valence is completely delocalized. The Creutz–Taube complex is an example of this class of complexes. These species also exhibit an IT band. Each site exhibits an intermediate oxidation state, which can be
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preparation, an iron(II) solution is mixed with an iron(III) cyanide (c-linked) complex. An electron-transfer reaction occurs via the cyanide ligands to give iron(III) associated with an iron(II)-cyanide
384:
Hazra, Susanta; Sasmal, Sujit; Fleck, Michel; Grandjean, Fernande; Sougrati, Moulay T.; Ghosh, Meenakshi; Harris, T. David; Bonville, Pierre; Long, Gary J.; Mohanta, Sasankasekhar (2011-05-07).
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for their interconversion. Some thermal activation is required to induce electron transfer from one site to another via the bridge. These species exhibit an intense
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Organic mixed valence compounds are also known. Mixed valency in fact seems to be required for organic compounds to exhibit electrical conductivity.
310:
Brunschwig, Bruce S.; Creutz, Carol; Sutin, Norman (2002). "Optical transitions of symmetrical mixed-valence systems in the Class II–III regime".
386:"Slow magnetic relaxation and electron delocalization in an S = 9/2 iron(II/III) complex with two crystallographically inequivalent iron sites"
248:
Demadis, Konstantinos D.; Hartshorn, Chris M.; Meyer, Thomas J. (2001). "The
Localized-to-Delocalized Transition in Mixed-Valence Chemistry".
439:
Dutta, Sujit K.; Ensling, Jürgen; Werner, Rüdiger; Flörke, Ulrich; Haase, Wolfgang; Gütlich, Philipp; Nag, Kamalaksha (1997-02-03).
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is a robust, readily analyzed, mixed-valence complex consisting of otherwise equivalent Ru(II) and Ru(III) centers bridged by the
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221:
Cowan, D. O.; LeVanda, C.; Park, J.; Kaufman, F. (1973). "Organic Solid State. VIII. Mixed-Valence
Ferrocene Chemistry".
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347:"Synthesis and x-ray crystal structures of tetranickel and tetrazinc complexes of a macrocyclic tetranucleating ligand"
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Class II, which are intermediate in character. There is some localization of distinct valences, but there is a low
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54:
478:
Richardson, D. E.; Taube, H. (1984). "Mixed-Valence
Molecules: Electronic Delocalization and Stabilization".
125:. There are distinct sites with different specific valences in the complex that cannot easily interconvert.
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66:
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507:"Réexamen de la structure du complexe hexaméthylène-tétrathiafulvalène-tétracyanoquinodiméthane"
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441:"Valence-Delocalized and Valence-Trapped FeIIFeIII Complexes: Drastic Influence of the Ligands"
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Bell, M.; Edwards, A. J.; Hoskins, B. F.; Kachab, E. H.; Robson, Richard (May 1989).
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complex in which there is an iron(II) atom surrounded by six carbon atoms of six
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174:. This complex serves as a model for the bridged intermediate invoked in
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Class I, where the valences are trapped—localized on a single site—such as
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Mixed-valence compounds are subdivided into three groups, according to the
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ligands bridged to an iron(III) atom by their nitrogen ends. In the
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Robin, Melvin B.; Day, Peter (1967). "Mixed
Valence Chemistry".
194:/TCNQ charge transfer salt, which features mixed valency.
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D. Chasseau; G. Comberton; J. Gaultier; C. Hauw (1978).
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Edge-on view of the crystal structure of hexamethylene
445:Angewandte Chemie International Edition in English
285:Advances in Inorganic Chemistry and Radiochemistry
53:. Well-known mixed valence compounds include the
38:is classified as type II mixed valence complex.
8:
538:Hankache, Jihane; Wenger, Oliver S. (2011).
98:that is also mixed-valence (Ru(II)Ru(III)).
65:. Many solids are mixed-valency including
81:The structure of the Creutz-Taube complex.
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351:Journal of the American Chemical Society
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49:which is present in more than one
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511:Acta Crystallographica Section B
390:The Journal of Chemical Physics
182:Mixed valence organic compounds
480:Coordination Chemistry Reviews
176:inner-sphere electron transfer
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297:10.1016/S0065-2792(08)60179-X
223:Accounts of Chemical Research
492:10.1016/0010-8545(84)85063-8
134:Intervalence charge transfer
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524:10.1107/S0567740878003830
27:Type of chemical compound
312:Chemical Society Reviews
104:Robin–Day classification
73:Robin–Day classification
540:"Organic Mixed Valence"
43:Mixed valence complexes
457:10.1002/anie.199701521
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18:Mixed valence compound
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168:Creutz–Taube complex
96:coordination polymer
67:indium chalcogenides
55:Creutz–Taube complex
36:biferrocenium cation
363:10.1021/ja00192a018
235:10.1021/ar50061a001
140:is an iron(II,III)–
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123:antimony tetroxide
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556:10.1021/cr100441k
402:10.1063/1.3581028
357:(10): 3603–3610.
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130:activation energy
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486:: 107–129.
291:: 247–422.
45:contain an
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517:(2): 689.
208:References
465:0570-0833
410:0021-9606
371:0002-7863
589:Electron
564:21574545
418:21548699
332:12122642
270:11749392
172:pyrazine
153:complex.
229:: 1–7.
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142:cyanide
47:element
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