Chemistry 250: Rethinking Chemical Bonds

Trends:Electronegativity Lewis Structures to VSEPR and Beyond

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

2 > DX > 0.5 : polar

DX < 0.5 : covalent
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Electronegativity, X
Paulings definition:

(note: DHd (A-B) = D(A-B))

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)

D(A-B) = D(A-B),experimental - D(A-B),theory

XA XB = 0.102 (D(A-B))
0.0104 is a conversion from kJ/mol to eV. Then 0.102 = (0.0104)1/2,. If D(A-B) is in eV, no conversion needed

A-B

A+ B-

An example calculation for H-F

Q) The bond dissociation energies of H2, F2 and HF are 436, 158 and 566 kJ/mol respectively. Estimate the electronegativity of H using Paulings method. D(H-F),theory = (D(H-H) + D(F-F)) = (436 + 158) = 297 kJ/mol D(H-F) = D(H-F),experimental - D(H-F),theory = 566 297 = 269 kJ/mol XF XH = 0.102 (D(H-F)) = 0.102 (269) = 1.67 (0.102 converts to eV)

Pauling set XF = 4.0 so: XH = 4.0 1.67 = 2.32

Note: 2.32 is different than the value of 2.2 you see in tables because Pauling used the geometric mean instead of the arithmetic mean for this value. Pauling comments that it is more accurate to use the geometric mean rather than the arithmetic mean, but then uses the arithmetic mean himself most of the time. Geometric mean of a and b = (a x b)0.5 Here it gives D (H-F) = 262.5 kJ/mol.

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

(note: DHie A = IPA)

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

XA XB = ([IPA + EAA] [IPB + EAB])

XA = ([IPA + EAA]) (these are then scaled to fit the 0-4 scale)

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

The Allred-Rochow definition:

The assumption is that the force that will draw an electron toward an atom is proportional to the effective nuclear charge of that atom and related to the distance of the electron from the nucleus. Z* = effective nuclear charge 2 Z*e e = charge of electron Force 0 = permittivity of a vacuum 40r 2 r = atomic radius The equation:

X = 0.359 (Z*/r2) + 0.744

puts the calculated values on the Pauling scale. This definition is useful because it can be applied to many more atoms and is one of the most used scales.
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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

Diagonal relationship in (X); comparable electronegativities between C, P, Se, I etc.

Electronegativity also lets us predict the polarity of bonds and chemical reactivity.
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Models of Bonding: G.N. Lewis (published 1916)

H Li Na K Rb Cs Be Mg Ca Sr Ba B Al Ga In Tl C Si Ge Sn Pb N P As Sb Bi O S Se Te Po F Cl Br I At He Ne Ar Kr Xe Rn
Gilbert N. Lewis, Berkeley, 1873-1946.

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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Lewis: Octet Rule and ionic compounds

Metals lose electrons: Na(1s22s2sp63s1) Na+ (1s22s22p6) + e Non-metals gain electrons: O(1s22s22p4) + 2 e O2(1s22s22p6) The resultant ions are attracted to each other to form ionic bonds (e.g. Na2O)

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Lewis Octets and Covalent Compounds

F F C F F F N F F F O F F F

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

does not satisfy octet rule for carbon

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

Formal Charges at a Glance

O O N N N C C C C

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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Exceptions to Octet Rule 1

F F B F Cl BeCl2 (g) Be Cl

F B F F Best Lewis structure

F B F F and 2 other resonance structures Cl Be Cl Cl -2 Be Cl

Best Lewis structure

just plain silly

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)

Exceptions to the Octet 2: Hypervalent Compounds

F F S F S(II) F F S F S(IV) O P H3C CH3 CH3 P(III) H3C P CH3 CH3 P(V) F F F Br F Br(V) F F F F F F F F S F S(VI) Cl(I) F Cl F F Cl F Cl(III) F F I F F F

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 trigonal tetrahedral bipyramidal

X octahedral

R.J. Gillespie, McMaster VSEPR protagonist.

line

triangle

tetrahedron

trigonal bipyramid

octahedron
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The geometry around an atom is described by the general formula:

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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Three and Four Objects Examples

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

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VSEPR Examples: Five Objects

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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Electron Pair Domains

Qualitatively, electron pairs are most probably found at a particular location, but occupy a domain Strength of repulsion relates to domain size: Lone pair - lone pair > lone pair bond pair > bond pair bond pair Lone pairs dont look like bunny ears. They are closer to the nucleus than bonding pairs, and thus take up more space in the valence shell.
Lone pair of electrons

Increasing steric demand

Multiple bond polarized toward central atom Normal single bond

Long single bond polarized away from central atom

111.7

N
104.5

109.5

CH4

106.6o NH3

OH2

Yellow is central atom

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More VSEPR Predictions

F 173o F o 101 S F F F Cl F F 87.5o F Xe F F 81o F Xe F

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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VSEPR Examples: Six and Seven Objects

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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A Physical Basis for the VSEPR Model

2-D "thought experiment" 3 spin add 3 spin up down electrons electrons on a ring

H+
add H+

H+

H+

add H+(looks like AX2E, e.g. H2C:)

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

Experimental Evidence for Electron-Pair Localization? N2

Contour map for N2

Relief Map for N2

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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Experimental Evidence for Electron-Pair Localization? H2O

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

Second-Derivatives and the Laplacian?

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

Laplacian of Ne: quantum shells

Ne atom electron density

Laplacian of electron density Ne 1s22s22p6 Note: no localized lone pairs for Ne, perfectly spherical atom Laplacian produces maxima for the quantum shells (here the n=1 and n=2 (outer) shells appear as maxima

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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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Documented Exceptions to VSEPR

Tetrahedral angle is 109.5o. AX2E2 bond angles should be lower.

Historically, strong Si-O bonds and large Si-O-Si bond angles in disiloxane was rationalized by use of 3d-orbitals on Si. No supporting evidence for this. As bonds become increasingly ionic, electrons are less localized, and steric repulsions dominate

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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Problems with the Our Model of Bonding: Photoelectron Spectrum of CH4

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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Troubles with Dioxygen (O2)

O O
pair electrons happy octets

oxygen atoms 6 electrons each

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.

But what about the failure with O2 , CH4?

Next class: Applying atomic orbitals to bonding
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