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Electronegativity, X Pauling (1932): Describes the ability of an atom (or functional group) in a molecule to attract electron density in a bond.
Linus Pauling
First Year rule DX > 2 : ionic Traditional scale goes from 0 to 4 with X of F set to 4; kept all values positive
Electronegativity, X
Paulings definition:
The dissociation energy of a purely covalent bond A-B should be the mean of the dissociation energies for the homonuclear bonds A-A and B-B. Any additional energy must be caused by electrostatic attraction between A and B (attributed to ionic character in a bond). The ionic character must be related to the difference in the electronegativities of A and B. He calculated this difference as follows: D(A-B) is the ionic resonance energy D(A-B),theory = (D(A-A) + D(B-B)) in kJ/mol (D(A-B) is in eV)
A-B
A+ B-
Similar calculations were used to determine X for the other elements. (D(H-Cl) ) = 0.98 eV relative to H so XCl 3.2 (D(H-Br) ) = 0.73 eV relative to H so XBr 2.9 (D(H-I) ) = 0.25 eV relative to H so XI 2.5
Electronegativity, X
Mullikens definition:
Mulliken figured that the electronegativity of an element must be related to the energies of gaining and losing electrons. Specifically an atom that binds its electrons stongly (large DHie) and gains other electrons readily (very positive EA or very negative DHea) should do the same in molecules. Thus Mulliken calculated the electronegativity of an atom as the mean of the ionization potential and the electron affinity. For A-B, the electronegativity difference between A+B- and A-B+ is given by:
Robert Mulliken
This method makes a lot of sense, but is not used because values of DHea 5 have not been accurately determined for many elements.
Electronegativity, X
Electronegativity, X
There are several other definitions based on different assumptions and methods, such as quantum mechanical calculations (Boyd) or spectroscopic measurements (Allen), but the values for elements usually end up around the same.
Electronegativity: Numbers
Proposal: In compounds, atoms achieve noble-gas electron configurations by electron loss or gain, or sharing of one or more pairs of electrons.
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F F C F F F N F F F O F Lewis Structures F F
Pairs of valence electrons arranged as nonbonding and 11 bonding, with a line between atoms used to depict the latter.
Multiple Bonds
O C O N N C C O O N C O O O
Lewis Structures show formal charges on atoms formal charge = # of e- from neutral atom (# of nonbonding e + 1/2 # of shared bonding e-) for carbon in CO = 4 - (2+3) = -1 C O for oxygen in CO = 6 - (2+3) = +1 Bond orders typically correlate with bond length and strength 12
N C
Not too many different possibilities, so pretty easy to remember after a few examples Same holds true for heavier elements
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Avoid assigning unrealistic formal charges (e.g. +ve charge on the most electronegative element, F; ve charges on metals like Be) Low electron count often reflects reactivity (e.g. BF3 is a14 good Lewis acid, BeCl2 not monomeric in the solid-state)
F(VII)
Never with N, O, F as the hypervalent element! Common with more electronegative elements (O,F) supporting a hypervalent heavier main group element 15 Note the least electronegative atom is the central one!
Common Errors
3 O + N + 1 e = 24 electrons O N O A O O 2+ O N O B O N O C O O N O D O
Which of the resonance structures are unreasonable for NO3? What is the N-O bond order?
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Valence Shell Electron Pair Repulsion (VSEPR) Theory of Molecular Geometry (1957)
Bonding pairs (single or multiple) and nonbonding pairs in the valence shell stay as far apart as possible. Central atom A, bonded atoms X, lone pairs E.
X A X X linear X A X trigonal planar X X A X X X X A X X X X X A X X
X octahedral
line
triangle
tetrahedron
trigonal bipyramid
octahedron
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AXmEn
Where X is a bonded atom, E is a lone pair and (m+n) is the number of objects (sometimes called the steric number, SN) around the central atom A.
Number of Objects Geometry Formula (Shape) 3 trigonal planar AX3 (trig. planar) AX2E (bent) 4 tetrahedral AX4 (tetrahedral) AX3E (pyramidal) AX2E2 (bent) 5 trigonal bipyramidal AX5 (t.b.p. or square pyramidal) AX4E (seesaw) AX3E2 (T-shaped) AX2E3 (linear) 6 octahedral AX6 (octahedral) AX5E (square pyramidal) AX4E2 (square planar) AX3E3 (T-shaped)
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Single bonds, double bonds and lone pairs all treated as objects in the valence sphere
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Aside: Neil Bartlett (1932-2008) and Chemistry of the Not so Inert Gases
20 20
Larger lone pair occupies more spacious equatorial positions. Both axial and equatorial have the same closest angle to other sites equal to 90o, but equitorial has fewer (2 versus 3)
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111.7
N
104.5
109.5
CH4
106.6o NH3
OH2
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Note deviation from ideal geometries Rationalized by size of lone pairs versus bonding pairs Xe-F bond more polarized towards F, larger valence shell than Cl
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AX4E2 features 2 lone pairs; they stay as far apart as possible With 7-coordinate structures, there are several possible geometries of similar energy; not always easily predicted What deviations from ideal geometry are expected for BrF5?
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2-D "thought experiment" 3 spin add 3 spin up down electrons electrons on a ring
H+
add H+
H+
H+
2-D example: 6 electrons on a ring. Combine electrostatic repulsion with the fact that electrons of the same spin will not occupy the same regions in space (a result of the Pauli Exclusion Principle) The Repulsion in VSEPR is not electrostatic! Strangely, it is not a force at all that repels electron pairs, it is the requirements of the Pauli Principle. The effect of the Pauli Principle is often ignored in modern MO-based (molecular orbital) discussions of bonding (for no obvious reason). 25
Magnified
Electron densities have units e/3 An observable; it can be measured (e.g. single crystal X-ray diffraction). A function (has a value) at coordinates x,y,z. Hard to show in 2-dimensions. All maxima are at nuclei, with a saddle between bonded nuclei. Where are the lone pairs?
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y
Electron density in xy-plane: Contour map and relief plot
z
Electron density line plot in xz plane. Triangle marks projections out of plane hydrogens Notice distortion around oxygen in xz-plane. Football shape, but no nuclear 27 attractors in these directions
Negative of second derivative called Laplacian Areas of local concentration are maxima (where point is greater than average of adjacent points) What would this look like for electron densities?
A MAXIMUM at x1!
ve of 2nd derivative 28
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Laplacian of H2O
z
Electron density line plot in xz plane. Triangle marks projections out of plane hydrogens
Laplacian of electron density relief map in xz plane. Maxima are exactly where lone pairs are expected
Laplacian of electron density reveals maxima that are exactly where lone pairs are expected.
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Although the original VSEPR model did not take steric repulsion into account, there a few examples where ligands can be considered close packed, and steric effects cannot be ignored.
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Note: 1s2 core electrons on C are much lower in energy, these are just the valence electrons Why 2 bands (at 23 eV, and 12.7 eV)? Arent all the bonding electrons in the same energy orbitals?
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O O
pair electrons happy octets
Correctly predicts O2 bond order of 2 (1.21 O=O distance versus around 1.48 for a O-O single bond)
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Summary
Concept: Electronegativity, very useful in bonding and reactivity Lewis structures and VSEPR:
I expect you to be able to: -Draw Lewis structures (including resonance structures when necessary), determine bond orders, determine and place formal charges. -Predict VSEPR geometries and deviations from ideal geometry. -Lots of examples of the 3-D geometries of molecules are on the CLEW site. Test your skills! Practice until it is easy.