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i-Clicker 24-1:
Technetium is a rare element found on earth with isotopes that can be used in medical testing. Which of the following is the correct ground state electron configuration of Tc4+?
electrons we are filling the d orbitals in the shell below the valence
Group 1B and some others have 1 valence electron due to promotion of an electron into the d sublevel to fill it form ions by losing the ns electrons first, then the (n 1)d
Coordination Compounds
When a complex ion combines with counter-ions to
make a neutral compound it is called a coordination compound The primary valence is the oxidation number of the metal The secondary valence is the number of ligands bonded to the metal
coordination number
Coordination Compounds
3+ Ligands
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Common Ligands
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i-Clicker 24-2:
A. pentaamminechloroplatinum(IV) tribromide B. triamminechloroplatinum(IV) bromide C. pentaamminebromoplatinum(IV) chloride D. pentaamminechloroplatinum(IV) bromide E. Chloropentaammineplatinum(IV) bromide
i-Clicker 24-3:
Isomers
Structural isomers are molecules that have the
same number and type of atoms, but they are attached in a different order Stereoisomers are molecules that have the same number and type of atoms, and that are attached in the same order, but the atoms or groups of atoms point in a different spatial direction
Tro, Chemistry: A Molecular Approach 19
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Linkage Isomers
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Geometric Isomers
geometric isomers are stereoisomers that differ
in the spatial orientation of ligands
cis-trans fac-mer isomerism cis-trans isomerism isomerismin in inoctahedral octahedral square-planar complexes complexes complexes MA MA3 MA B3 4B 2 2B2
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Ex. 24.5 Draw the structures and label the type for all isomers of [Co(en)2Cl2]+
the ethylenediamine ligand (en = H2NCH2CH2NH2) is bidentate each Cl ligand is monodentate octahedral MA4B2
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[Co(en)3]3+
Optical Isomers
optical isomers are
stereoisomers that are nonsuperimposable mirror images of each other
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Bonding in Coordination Compounds Electrostatic Model Overly Simplistic but USEFUL! Works well for Main Group metal complexes. Assumes a purely ionic attraction between the
central metal ion and charged or partially charged polar ligands. It predicts ligand-metal bonds will increase in strength with increasing charge density on the central metal atom. Al(H2O)63+ > Mg(H2O)62+
Tro, Chemistry: A Molecular Approach 26
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i-Clicker 24-4:
Which forms the strongest ligand-metal ion bond?
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4 6
More sophisticated model than the electrostatic model. More accurate than the Valence Bond Theory. Still simple enough for general utility. Assumes that ligands retain their electrons and central ions retain their electrons. Assumes that the d-electrons in the metal atoms are influenced (repelled) by the electron pairs in the ligands.
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ligand for the charge on the metal cation Electrons on the ligands repel electrons in the unhybridized d orbitals of the metal ion The result is the energies of orbitals the d sublevel are split The difference in energy depends the complex and kinds of ligands
Crystal field splitting energy Strong field splitting and weak field splitting
Tro, Chemistry: A Molecular Approach 35
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orbitals depends on the strength of the crystal field The 4th and 5th electrons will go into the higher energy dx2-y2 and dz2 if the field is weak and the energy gap is small leading to unpaired electrons and a paramagnetic complex The 4th thru 6th electrons will pair the electrons in the dxy, dyz and dxz if the field is strong and the energy gap is large leading to paired electrons and a diamagnetic complex
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diamagnetic
paramagnetic
high-spin complex
low-spin complex
Only electron configurations d4, d5, d6, or d7 can have low or high spin
Tro, Chemistry: A Molecular Approach 42
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d8 metals the most complex splitting pattern most are low-spin complexes
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Electron Jumping
For transition metal complexes , the splitting between the d orbital energies in the crystal field corresponds to the energies of visible light Absorption of light raises an electron from a lower energy d orbital to a higher energy d orbital in the crystal field
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Green-Blue Observed
Light
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The absorbed energy is used to promote and electron from a lower energy orbital to a higher energy one
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Titanium Dioxide
TiO2 is the white pigment used in paper and paint Why is it white? Ti4+ has no d-electrons
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More Peculiarities
Different complexes can exhibit different colours even when the central transition metal is in the same oxidation state How does this happen?
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Spectrochemical Series
Orbital Diagrams
For octahedral d1 d3 all complexes are high spin all electrons in the lower energy d subshells
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Orbital Diagrams
The situation is more complex for d4 d7 complexes
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Spectrochemical Series
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Spectrochemical Series
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Problem
1. Calculate the CFSE for both high spin and low spin octahedral complexes of Co(gly)63-. Which is preferred? = 21, 476 cm-1, P = 23,625 cm-1,
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Problem 2
What is t if the compound absorbs at 690 nm? Solution: = 690 nm (1m/109 nm) = 6.90 x 107 m
= hc/ = (6.626 x 1034 Js)(2.998 x 108 m/s) 6.90 x 107 m = 2.88 X 10-19 J
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chemical analysis
qualitative analysis for metal ions
blue = CoSCN+ red = FeSCN2+
Tro, Chemistry: A Molecular Approach 73
biomolecules
porphyrin ring cytochrome C hemoglobin chlorphyll
Tro, Chemistry: A Molecular Approach
chlorophyll
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