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Chapter 9
Coordination
Chemistry I
Structures
and Isomers
Coordination compounds
• Central metal, neutral or cation
• Ligand: neutral molecule or anion
• Ions for charge balance (if necessary)
• Coordination number = number of ligand attachments
(commonly 4, 6, 5)
• Geometric and optical isomers possible
• Kf values: usually very large, >1010
Naming Coordination Compounds
• Cation + anion
• Ligands + metal in coordination compound
• Charge indicated by Roman numerals in
parentheses
• If complex ion carries a negative charge, add -ate
to the name of the metal
• Ligands are named in alphabetical order
• Prefixes indicate the number of ligands
Naming Ligands
• Neutral - aqua, ammine, carbonyl
• Anion - chloro, nitro, sulfato
• Cations are not common
• Chelating - multidentate
ethylenediamine
EDTA
acac
• Prefix if ligand is “complex” (neutral or name
contains a prefix)
2 (bis), 3 (tris), 4 (tetrakis)
Some examples...
• Pt(NH3)4
2+
• [Co(NH3)4(H2O)2]Cl2
• Ligands shown in Tables in Chapter 9
• Bridging ligands - μ
• Naming rules in Chapter 9
• Exercises 9-1 and 9-2
Common Structures
• CN 1, 2, 3 - follow VSEPR
Bulky ligands, filled d-orbitals
Ag(I), Cu(I), Au(I)
• CN 4 - Tetrahedral or Square Planar
d10 - tetrahedral; d8 - square planar
• CN 5 - trigonal bipyramid or square pyramid
Similar energy
• CN 6 - octahedral + distorted octahedron
• CN 7, 8, ... more unusual, but known
Coordination Compound Isomers
• Stereoisomers
geometric and optical isomers
• Structural
hydrate, solvent, ionization, linkage isomers
Geometric Isomers
• CN 4 and 6 most common
• cis, trans
• fac, mer
• Isomer designations for compounds containing
chelating ligands can get complicated (see
textbook), we will not use
Geometric + Optical Isomers
• Octahedral geometry (consider monodentate
ligands only): trans-pair method
• Mabcdef: Identify all trans pairs, then identify
optically active isomers
(ab)(cd)(ef), (ab)(ce)(df), (ab)(cf)(de), ......
• Try Ma2b2cd
• Diastereomer + mirror image = pair of enantiomers
• Bidentate ligands? Use capital letters or “manual”
method to identify geometric isomers
• M(AA)(BB)c2
• How many isomers? How many chiral isomers?
14
Structural isomers
• What is inside the coordination sphere?
• CrCl3
.6H2O has three hydrate isomers: non,
mono, and di-hydrate
• Coordination isomers differ in what is inside the
coordination sphere of each metal
[Pt(NH3)4][PtCl4] vs. [PtCl(NH3)3][Pt(NH3)Cl3]
• Ionization isomers give different number of ions
in solution or different ions in solution
[Co(NH3)4(NO2)Cl]Cl
[Co(NH3)4Cl2]NO2
Linkage
• Atom bonding to metal changes
• NO2
-
• M-NO2 - nitro
M-ONO - nitrito
• Can be converted by gentle heating
• SCN- bonds through S or N
• DMSO - S or O
17
Chapter 10: Bonding
18
19
Experimental Evidence: Magnetic
Susceptibility
20
Magnetic Susceptibility
g = constant
S = spin quantum number (multiplicity) = 2(total spin) + 1
L = sum of the highest possible ml values following Hund’s rule
21
Magnetic Susceptibility
22
Do some examples:
23
24
25
26
27

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fdocuments.in_chapter-9-coordinatin-chemistry-i.ppt

  • 2. Coordination compounds • Central metal, neutral or cation • Ligand: neutral molecule or anion • Ions for charge balance (if necessary) • Coordination number = number of ligand attachments (commonly 4, 6, 5) • Geometric and optical isomers possible • Kf values: usually very large, >1010
  • 3. Naming Coordination Compounds • Cation + anion • Ligands + metal in coordination compound • Charge indicated by Roman numerals in parentheses • If complex ion carries a negative charge, add -ate to the name of the metal • Ligands are named in alphabetical order • Prefixes indicate the number of ligands
  • 4. Naming Ligands • Neutral - aqua, ammine, carbonyl • Anion - chloro, nitro, sulfato • Cations are not common • Chelating - multidentate ethylenediamine EDTA acac • Prefix if ligand is “complex” (neutral or name contains a prefix) 2 (bis), 3 (tris), 4 (tetrakis)
  • 5.
  • 6.
  • 7.
  • 8. Some examples... • Pt(NH3)4 2+ • [Co(NH3)4(H2O)2]Cl2 • Ligands shown in Tables in Chapter 9 • Bridging ligands - μ • Naming rules in Chapter 9 • Exercises 9-1 and 9-2
  • 9. Common Structures • CN 1, 2, 3 - follow VSEPR Bulky ligands, filled d-orbitals Ag(I), Cu(I), Au(I) • CN 4 - Tetrahedral or Square Planar d10 - tetrahedral; d8 - square planar • CN 5 - trigonal bipyramid or square pyramid Similar energy • CN 6 - octahedral + distorted octahedron • CN 7, 8, ... more unusual, but known
  • 10. Coordination Compound Isomers • Stereoisomers geometric and optical isomers • Structural hydrate, solvent, ionization, linkage isomers
  • 11. Geometric Isomers • CN 4 and 6 most common • cis, trans • fac, mer • Isomer designations for compounds containing chelating ligands can get complicated (see textbook), we will not use
  • 12. Geometric + Optical Isomers • Octahedral geometry (consider monodentate ligands only): trans-pair method • Mabcdef: Identify all trans pairs, then identify optically active isomers (ab)(cd)(ef), (ab)(ce)(df), (ab)(cf)(de), ...... • Try Ma2b2cd • Diastereomer + mirror image = pair of enantiomers • Bidentate ligands? Use capital letters or “manual” method to identify geometric isomers • M(AA)(BB)c2 • How many isomers? How many chiral isomers?
  • 13.
  • 14. 14
  • 15. Structural isomers • What is inside the coordination sphere? • CrCl3 .6H2O has three hydrate isomers: non, mono, and di-hydrate • Coordination isomers differ in what is inside the coordination sphere of each metal [Pt(NH3)4][PtCl4] vs. [PtCl(NH3)3][Pt(NH3)Cl3] • Ionization isomers give different number of ions in solution or different ions in solution [Co(NH3)4(NO2)Cl]Cl [Co(NH3)4Cl2]NO2
  • 16. Linkage • Atom bonding to metal changes • NO2 - • M-NO2 - nitro M-ONO - nitrito • Can be converted by gentle heating • SCN- bonds through S or N • DMSO - S or O
  • 18. 18
  • 20. 20 Magnetic Susceptibility g = constant S = spin quantum number (multiplicity) = 2(total spin) + 1 L = sum of the highest possible ml values following Hund’s rule
  • 23. 23
  • 24. 24
  • 25. 25
  • 26. 26
  • 27. 27