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Chapter 20

Chapter 20. Transition Metals and Coordination Chemistry. Chapter 20: Transition Metals and Coordination Chemistry. 20.1 The Transition metals: A Survey 20.2 The First-Row Transition Metals 20.3 Coordination Compounds 20.4 Isomerism

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Chapter 20

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  1. Chapter 20 Transition Metals and Coordination Chemistry

  2. Chapter 20: Transition Metals and Coordination Chemistry 20.1 The Transition metals: A Survey 20.2 The First-Row Transition Metals 20.3 Coordination Compounds 20.4 Isomerism 20.5 Bonding in Complex Ions: The localized Electron Model 20.6 The Crystal Field Model 20.7 The Molecular Orbital Model 20.8 The Biological Importance of Coordination Complexes

  3. Vanadium metal (center) and in solution as V2+(aq), V3+(aq), VO2+(aq), and VO2+(aq), (left to right).

  4. Figure 20.1: Transition elements on the periodic table

  5. Calcite with traces of Iron Source: Fundamental Photographs

  6. Quartz

  7. Wulfenite

  8. Rhodochrosite

  9. Aqueous solutions containing metal ions Co+2 Mn+2 Cr+3 Fe+3 Ni+2

  10. Molecular model: The CO(NH3)63+ ion

  11. Figure 20.2: plots of the first (red dots) and third (blue dots) ionization energies for the first-row transition metals

  12. Figure 20.3: Atomic radii of the 3d, 4d, and 5d transition series.

  13. Transition metals are often used to construct prosthetic devices, such as this hop joint replacement. Source: Science Photo Library

  14. Liquid titanium(IV) chloride being added to water, forming a cloud of solid titanium oxide and hydrochloric acid.

  15. Colors of Representative Compounds of the Period 4 Transition Metals b d f h j g a c e i a = Scandium oxide b = Titanium(IV) oxide c = Vanadyl sulfate dihydrate d = Sodium chromate e = Manganese(II) chloride tetrahydrate f = Potassium ferricyanide g = Cobalt(II) chloride hexahydrate h = Nickel(II) nitrate hexahydrate i = Copper(II) sulfate pentahydrate j = Zinc sulfate heptahydrate

  16. Orbital Occupancy of the Period 4 Metals–I Element Partial Orbital Diagram Unpaired Electrons 4s 3d 4p Sc 1 Ti 2 V 3 Cr 6 Mn 5

  17. Orbital Occupancy of the Period 4 Metals–II Element Partial Orbital Diagram Unpaired Electrons 4s 3d 4p Fe 4 Co 3 Ni 2 Cu 1 Zn 0

  18. Oxidation States and d-Orbital Occupancy of the Period 4 Transition Metals 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B Oxidation (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) State Sc Ti V Cr Mn Fe Co Ni Cu Zn 0 0 0 0 0 0 0 0 0 0 0 (d1) (d2) (d3) (d5) (d5) (d6) (d7) (d8) (d10) (d10) +1 +1 +1 +1 +1 +1 +1 (d3) (d5) (d5) (d7) (d8) (d10) +2 +2 +2 +2 +2 +2 +2 +2 +2 +2 (d2) (d3) (d4) (d5) (d6) (d7) (d8) (d9) (d10) +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 (d0) (d1) (d2) (d3) (d4) (d5) (d6) (d7) (d8) +4 +4 +4 +4 +4 +4 +4 +4 (d0) (d1) (d2) (d3) (d4 ) (d5) (d6) +5 +5 +5 +5 +5 (d0) (d1) (d2) (d4) +6 +6 +6 +6 (d0) (d1) (d2) +7 +7 (d0)

  19. Figure 20.4: Titanium bicycle

  20. Figure 20.5: Structures of the chromium (VI) anions

  21. Manganese nodules on the sea floor Source: Visuals Unlimited

  22. Aqueous solution containing the Ni2+ ion

  23. Alpine Pennycress This plant can thrive on soils contaminated with Zn and Cd, concentrating them in the stems, which can be harvested to obtain these elements. Source: USDA photo

  24. Figure 20.6: Ligand arrangements for coordination numbers 2, 4, and 6

  25. Figure 20.7: a) Bidentate ligand ethylene-diamine can bond to the metal ion through the lone pair on each nitrogen atom, thus forming two coordinate covalent bonds. B) Ammonia with one electron pair to bond. a) b)

  26. Figure 20.8: The coordination of EDTA with a 2+ metal ion.

  27. Rules for Naming Coordination Compounds - I • As with any ionic compound, the cation is named before the anion • In naming a complex ion, the ligands are named before the metal ion. • In naming ligands, an o is added to the root name of an anion. For • example, the halides as ligands are called fluoro, chloro, bromo, and • iodo; hydroxid is hydroxo; and cyanide is cyano. For a neutral the • name of the molecule is used, with the exception of H2O, NH3, CO, • and NO, as illustrated in table 20.14. • 4) The prefixes mono-, di-, tri-, tetra-, penta-, and hexa- are used to • denote the number of simple ligands. The prefixes bis-, tris-, tetrakis-, • and so on, are also used, especially for more complicated ligands or • ones that already contain di-, tri-, and so on. • 5) The oxidation state of the central metal ion is designated by a Roman • numeral in parentheses.

  28. Rules for Naming Coordination Compounds - II • When more than one type of ligand is present, ligands are named in • alphabetical order. Prefixes do not affect the order. • If the complex ion has a negative charge, the suffix –ate is added to • the name of the metal. Sometimes the Latin name is used to identify • the metal (see table 20.15).

  29. Example 20.1 (P 947) • Give the systematic name for each of the following coordination • compounds: • a) [Co(NH3)5Cl]Cl2 b) K3Fe(CN)6 c) [Fe(en)2(NO2)2]2SO4 • Solution: • Ammonia molecules are neutral, Chloride is -1, so cobalt is +3 • the name is therefore: • pentaamminechlorocobalt(III) chloride • 3 K+ ions, 6 CN- ions, therefore the Iron must have a charge of +3 • the complex ion is: Fe(CN)6-3, the cyanide ligands are cyano, the • latin name for Iron is ferrate, so the name is: • potassium hexacyanoferrate(III) • c) Four NO2-, one SO4-2, ethylenediamine is neutral so the iron is +3 • the name is therefore: • bis(ethylenediamine)dinitroiron(III) sulfate

  30. An aqueous solution of [Co(NH3)5Cl]Cl2

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