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Lecture C3aMicroscopic to Macroscopic, Part 3:
Hydrogen Bonding and Metal-Ligand Bonding
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C-H covalent bond in CH4 = 440 kJ mol-1
Last time we examined various types of noncovalent intermolecular interactions:
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a. ion-ionb. ion-dipolec. electric dipole-electric dipoled. magnetic dipole-magnetic dipolee. dispersion forcesf. hydrogen bondingg. metal-ligand bonding
Let's look at hydrogen bonding next!
Last time we examined various types of noncovalent intermolecular interactions...
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Noncovalent Intermolecular Interactions
f. hydrogen bonding
HF hydrogen bond energy - a whopping 40 kJ mol-1
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Hydrogen bonds are formed by electronegative atoms (e.g., O, N, F) sharing their lone pair electrons with hydrogen atoms.The electronegative donor creates a positively charged H atomthat can then interact with the electronegative acceptor.
f. hydrogen bonding
carboxylic acid dimer
δ+
δ+
δ-δ-
δ- δ-
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Both the donor and acceptor need to be a highly electronegative atom: e.g., O, N, F
H-bond: acceptor donor
NH-carbonyl O
OH-carbonyl O
NH-amine N
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Noncovalent Intermolecular Interactions
f. hydrogen bonding
The H-bond donor shares the Hydrogen atom; the acceptor shares the lone pair.
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OH stretching frequencies in Hydrogen Bonds
Formic Acid (R=H):OH 3570 cm-1 monomerOH 3080 cm-1 dimer
HFHF 3960 cm-1 monomerHF 3450 cm-1 hydrogen bonded
carboxylic acid dimer
Frequency decreases (smaller k), but the Intensity increases : Δμ/Δx is substantially larger when H-bonding occurs
Δν = 490 cm-1
Δν = 510 cm-1
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Water is highly hydrogen bonded
Hydrogen Bonding Networks
f. hydrogen bonding
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This structure was obtained from a combination of x-ray diffraction (for the oxygen atoms) and
neutron diffraction (for the hydrogen atoms).
There are 15 known phases of ice. Here is the crystal structure for the most familiar to us, Ice Ih (hexagonal ice).
dotted lines are hydrogen bonds
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Glucose is a molecule that has a lot of OH groups (5): C6H12O6 or C6H7O(OH)5
A six-membered ring sugar or carbohydrate molecule.Other sugars: fructose, sucrose, ribose.
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Cellulose is a polymer molecule created by linking many glucose units together.
Cellulose polymers can hydrogen bond with themselves in many ways, giving rigidity to the solid.
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Proteins can have many hydrogen bonds as well: e.g., beta sheet (anti-parallel) structure
NH-carbonyl O
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DNA is another polymer that hydrogen bonds with itself:
Every sugar unit has one offour nitrogenous bases attached:
G - GuanineC - CytosineA - AdenineT - Thymine
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DNA is another polymer that hydrogen bonds with itself:
Guanine and Cytosine can hydrogen bond to each other:
three hydrogen bonds
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DNA is another polymer that hydrogen bonds with itself:
Adenine and Thymine can hydrogen bond to each other:
two hydrogen bonds
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DNA is another polymer that hydrogen bonds with itself:
3D structure of DNA is a double helix.
AT
CG
GC
TA
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DNA is another polymer that hydrogen bonds with itself:
James Watson and Francis Crick first proposed the double helix model in 1953.
Their double-helix model was based on an X-ray diffraction image taken by Rosalind Franklin and Raymond Gosling in 1952.
We now call this the Watson-Crick model of DNA.
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a. ion-ionb. ion-dipolec. electric dipole-electric dipoled. magnetic dipole-magnetic dipolee. dispersion forcesf. hydrogen bondingg. metal-ligand bonding
Noncovalent Intermolecular Interactions
Final topic: lets's look at metal-ligand bonding!
Is it covalent or non-covalent?
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
Lone pairs of small molecules can interact with the d and f electrons of metals to form complexes. The small molecules are called “ligands.”
[Ni(H2O)6]2+ is green.
[Ni(NH3)6]2+ is violet.
In aqueous solution:
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Noncovalent Intermolecular Interactions
Multi-Ligand Molecules:
EDTA - H4Y
Ethylene diamine tetraacetic acid (EDTA)has six ligands and is a great metal chelator.
MYn-4Mn+ + Y4-
Ethylene diamine - en
NH2-CH2-CH2-NH2
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
Metal-CO (metal-carbonyls) are strong ligand bonds
CO HOMO (5σ) CO LUMO (1π*)
Both the CO HOMO and LUMO are involved in metal ligand bonding
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
Metal Carbonyls: "Pi back bonding"
Both the CO HOMO and LUMO are involved in metal ligand bonding
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
CO infrared stretch:
Back bonding to theHOMO reduces the bond order of CO, soa the CO stretchingfrequency is lowered inthe complexes
2143 cm-1 gas phase
Infrared Spectroscopy!
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
CO infrared stretch:
2143 cm-1 gas phase
Nickel Tetracarbonyl
Ni(CO)4
2059 cm-1 complex10 + (4 x 2) = 18 electron rule!
Ni: 4s23d8
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
Iron Pentacarbonyl
Fe(CO)5
CO infrared stretch:
2143 cm-1 gas phase
2022 and 2000 cm-1 complex8 + (5 x 2) = 18 electron rule!
Fe: 4s23d6
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
CO infrared stretch:
2000 cm-1 complex6 + (6 x 2) = 18 electron rule!
Cr: 4s13d52143 cm-1 gas phase
Cr(CO)6
Chromium Hexacarbonyl
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Metal carbonyl bonds in 18e systemsrange in energy from 100-200 kJ mol-1
Last time we examined various types of noncovalent intermolecular interactions:
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Noncovalent Intermolecular Interactions
g. metal-ligand bonding
Fe in Heme
There are many types of metal-ligand bonds, varying from very weak to very strong.
This is called Inorganic Chemistry!
Fe2+ or Fe3+