GENERAL CHEMISTRY PRINCIPLES AND MODERN APPLICATIONS ELEVENTH EDITION

Complex Ions and Coordination Compounds Slide 24 - 2 CONTENTS 24 -1 Werner’s Theory

Complex Ions and Coordination Compounds Slide 24 - 3 CONTENTS 24 -9 Acid-Base Reactions

24 -1 Werner’s Theory of Coordination Compounds: An Overview FIGURE 24 -1 Two coordination

[Co(NH 3)6]3+ [Co. Cl 4(NH 3)2]− Complex cation Complex anion [Co. Cl 3(NH 3)3]

FIGURE 24 -2 Structures of some complex ions Slide 24 - 6 General Chemistry:

24 -2 Ligands Slide 24 - 7 General Chemistry: Chapter 24 Copyright © 2017

Slide 24 - 8 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

FIGURE 24 -3 Three representations of the chelate [Pt(en)2]2+ Slide 24 - 9 General

24 -3 Nomenclature 1) Anions as ligands are named using the ending –o –ide

Slide 24 - 11 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -4 Isomerism Ionization Isomerism [Cr. Cl(NH 3)5]SO 4 [Cr(NH 3)5 SO 4]Cl Pentamminesulfatochromium

Linkage Isomerism [Co(NH 3)5(ONO)]2+ [Co(NO 2)(NH 3)5]2+ Pentaamminenitrito-N-cobalt(III) ion Pentaamminenitrito-O-cobalt(III) ion Geometric Isomerism [Pt.

FIGURE 24 -4 Linkage isomerism-illustrated Slide 24 - 14 General Chemistry: Chapter 24 Copyright

The geometric isomers of [Pt. Cl 2(NH 3)2] Slide 24 - 15 General Chemistry:

FIGURE 24 -5 Geometric isomerism-illustrated Slide 24 - 16 General Chemistry: Chapter 24 Copyright

FIGURE 24 -6 Cis and trans isomers of an octahedral complex Slide 24 -

The geometric isomers of [Co. Cl 3(NH 3)3] Slide 24 - 18 General Chemistry:

Optical Isomerism Figure 24 -7 Superimposable and nonsuperimposable objects–an open-top box Slide 24 -

FIGURE 24 -8 Optical Isomers Slide 24 - 20 General Chemistry: Chapter 24 Copyright

FIGURE 24 -9 Optical Activity Slide 24 - 21 General Chemistry: Chapter 24 Copyright

Isomerism and Werner’s Theory FIGURE 24 -10 Hypothetical strucutres for [Co. Cl 2(NH 3)4]+

24 -5 Bonding in Complex Ions: Crystal Field Theory FIGURE 24 -1 Approach of

FIGURE 24 -12 Splitting of d energy levels in the formation of an octahedral

low spin Slide 24 - 25 high spin General Chemistry: Chapter 24 Copyright ©

FIGURE 24 -13 Crystal field splitting in a tetrahedral complex ion Slide 24 -

Slide 24 - 27 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

FIGURE 24 -14 Comparison of crystal field splitting in a square-planar and an octahedral

24 -6 Magnetic Properties of Coordination Compounds and Crystal Field Theory FIGURE 24 -15

24 -7 Color and the Colors of Complexes Primary, Secondary and Complimentary Colors FIGURE

Colored Solutions FIGURE 24 -17 Light absorption and transmission Slide 24 - 31 General

FIGURE 24 -18 Effects of ligands on the colors of coordination compounds Slide 24

(24. 1) (24. 2) The displacement occurs in a stepwise fashion: (24. 3) (24.

(24. 1) (24. 2) K 1 is often designated β 1 and is called

(24. 1) (24. 2) The formation constants for all four ions in the series

Slide 24 - 36 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -9 Acid-Base Reactions of Complex Ions FIGURE 24 -19 Ionization of [Fe(H 2

24 -10 Some Kinetic Considerations light blue yellow in conc HCl light blue deep

FIGURE 24 -2 Inert complex ions Slide 24 - 39 General Chemistry: Chapter 24

24 -11 Applications of Coordination Chemistry Cisplatin: A Cancer-Fighting Drug trans-[Pt. Cl 2(NH 3)2]

Cisplatin enters the cell by diffusion and hydrolyses: + H 3 O + Cl−

Hydrates [Co(H 2 O)6](Cl. O 4) 2 Co(Cl. O 4)2 • 6 H 2

Stabilization of Oxidation States E° = +1. 82 V Co 3+ is a strong

Photography: Fixing a Photographic Film exposure defects in the crystal lattice fixing (24. 13)

Qualitative Analysis [Co(SCN)4]2− complex ion [Fe(H 2 O)4 (SCN)]2+ complex ion mixture of [Fe.

Sequestering Metal Ions 4 Na+ sodium salt of ethylenediaminetetraacetic acid (Na 4 EDTA) A

FIGURE 23 -23 Structure of a metal-EDTA complex Slide 24 - 47 General Chemistry:

Biological Applications: Porphyrins FIGURE 24 -24 The porphyrin structure Slide 24 - 48 General

FIGURE 24 -25 Structure of chlorophyll a Slide 24 - 49 General Chemistry: Chapter

End of Chapter Slide 24 - 50 General Chemistry: Chapter 24 Copyright © 2017

Slides: 50

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GENERAL CHEMISTRY PRINCIPLES AND MODERN APPLICATIONS ELEVENTH EDITION PETRUCCI HERRING MADURA BISSONNETTE Complex Ions and Coordination Compounds 24 PHILIP DUTTON UNIVERSITY OF WINDSOR DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY Slide 24 - 1 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Complex Ions and Coordination Compounds Slide 24 - 2 CONTENTS 24 -1 Werner’s Theory of Coordination Compounds: An Overview 24 -2 Ligands 24 -3 Nomenclature 24 -4 Isomerism 24 -5 Bonding in Complex Ions: Crystal Field Theory 24 -6 Magnetic Properties of Coordination Compounds and Crystal Field Theory 24 -7 Color and the colors of Complexes 24 -8 Aspects of Complex-Ion Equilibria General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Complex Ions and Coordination Compounds Slide 24 - 3 CONTENTS 24 -9 Acid-Base Reactions of Complex Ions 24 -10 Some Kinetic Considerations 24 -11 Applications of Coordination Chemistry General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -1 Werner’s Theory of Coordination Compounds: An Overview FIGURE 24 -1 Two coordination compounds Slide 24 - 4 General Chemistry: Chapter 24 Alfred Werner (1866 -1919) Copyright © 2017 Pearson Canada Inc.

[Co(NH 3)6]3+ [Co. Cl 4(NH 3)2]− Complex cation Complex anion [Co. Cl 3(NH 3)3] K 4[Fe(CN)6] Neutral complex Coordination compound Slide 24 - 5 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -3 Nomenclature 1) Anions as ligands are named using the ending –o –ide changes to–ido, –ite to –ito, and –ate to –ato. 2) Neutral molecules generally carry the unmodified name 3) The number of ligands is denoted by a prefix mono, di, tri, tetra, penta, hexa 4) Ligands are named first in alphabetical order followed by the name of the metal center. Oxidation state is denoted by a Roman numeral. Anions end the metal name in -ate 5) Formula is written with metal first, followed by the ligand symbols in alphabetical order 6) Cations come first, followed by anions Slide 24 - 10 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -4 Isomerism Ionization Isomerism [Cr. Cl(NH 3)5]SO 4 [Cr(NH 3)5 SO 4]Cl Pentamminesulfatochromium (III) chloride Pentamminechloridochromiium(III) sulfate Coordination Isomerism [Cr(NH 3)6][Co(CN)6] [Co(NH 3)6][Cr(CN)6] Hexaamminecobalt(III) hexacyanidochromate(III) Slide 24 - 12 Hexaamminechromium(III) hexacyanidocobaltate(III) General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Linkage Isomerism [Co(NH 3)5(ONO)]2+ [Co(NO 2)(NH 3)5]2+ Pentaamminenitrito-N-cobalt(III) ion Pentaamminenitrito-O-cobalt(III) ion Geometric Isomerism [Pt. Cl 2(NH 3)2] cis-diamminedichloridoplatinum(II) or trans-diamminedichloridoplatinum(II) Slide 24 - 13 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -5 Bonding in Complex Ions: Crystal Field Theory FIGURE 24 -1 Approach of six anions to a metal ion to form a complex ion with octahedral structure Slide 24 - 23 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

(24. 1) (24. 2) K 1 is often designated β 1 and is called the formation constant for [Zn(H 2 O)3 NH 3]2+ β 2 is the formation constant for [Zn(H 2 O)2(NH 3) 2]2+, the sum of (23. 3) and (23. 4) (24. 7) (24. 8) Slide 24 - 34 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

(24. 1) (24. 2) The formation constants for all four ions in the series are given by: Slide 24 - 35 [Zn(H 2 O)3 NH 3]2+ β 1 = K 1 [Zn(H 2 O)2(NH 3)2]2+ β 2 = K 1 K 2 [Zn(H 2 O)1(NH 3)3]2+ β 2 = K 1 K 2 K 3 [Zn(NH 3)4]2+ β 4 = K 1 K 2 K 3 K 4 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -10 Some Kinetic Considerations light blue yellow in conc HCl light blue deep blue pale green in dil. HCl FIGURE 24 -20 Labile complex ions Slide 24 - 38 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

24 -11 Applications of Coordination Chemistry Cisplatin: A Cancer-Fighting Drug trans-[Pt. Cl 2(NH 3)2] (transplatin) cis-[Pt. Cl 2(NH 3)2] (cisplatin) K 2[Pt. Cl 4] + 4 KI K 2[Pt. I 4] + 4 KCl K 2[Pt. I 4] + NH 3 + KI K 2[Pt. I 2(NH 3)] + NH 3 + KI treat with Ag. NO 3 followed by KCl to obtain cisplatin Slide 24 - 40 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Cisplatin enters the cell by diffusion and hydrolyses: + H 3 O + Cl− binds to cellular DNA Platinum based drugs have annual sales in excess of $2 B. Slide 24 - 41 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Hydrates [Co(H 2 O)6](Cl. O 4) 2 Co(Cl. O 4)2 • 6 H 2 O [Cu. SO 4] • 5 H 2 O [Cu(H 2 O)4][SO 4 • H 2 O] Ba. Cl 2 • 2 H 2 O KAl(SO 4)2 • 12 H 2 O Slide 24 - 42 lattice water In alums, some water is coordinated to an ion and some is lattice water General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Stabilization of Oxidation States E° = +1. 82 V Co 3+ is a strong oxidizing agent and oxidizes water to O 2 E°cell = +0. 59 V (24. 12) strong electron pair donors stabilize high oxidation states β 6 = Kf = 4. 5 1033 E° = +0. 10 V Slide 24 - 43 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Photography: Fixing a Photographic Film exposure defects in the crystal lattice fixing (24. 13) Black metallic Ag remains on the film, while the unexposed Ag. Br is removed. A negative image is created. Photographic paper is then exposed to light shining through the negative, and the same process then produces the corresponding positive image. Slide 24 - 44 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.

Qualitative Analysis [Co(SCN)4]2− complex ion [Fe(H 2 O)4 (SCN)]2+ complex ion mixture of [Fe. F 6] and [Co(SCN)4]2− complex ion FIGURE 24 -22 Qualitative tests for Co 2+ and Fe 3+ Slide 24 - 45 General Chemistry: Chapter 24 Copyright © 2017 Pearson Canada Inc.