Bonding in Molecules

Lecture 3

Molecular shapes

Known shape of some AH2 molecules Molecular species LiH2+ LiH2, BeH2+ BeH2, BH2+ BH2, AlH2, CH2+ CH2, SiH2, BH2-, NH2+ NH2, PH2, CH2-, OH2+ OH2, SH2, NH2-, FH2+ No. of valence electrons 2 3 4 5 6 7 8 Shape Bent Linear Linear Bent Bent Bent Bent

Molecular species BH2 CH2 SiH2 NH2 OH2 SH2 FH2+

angle 131 110 93 103 104.5 92.1 118

Dh

C2v

Walsh diagram

poorer overlap of H1s with 2px remains non-bonding

better overlap of H 1s orbitals First order effects

Walsh diagram

mixing can occur between 2 orbitals because they both transform as a1 in the lower symmetry

A second order effect (often called a second order Jahn Teller distortion)

1 E

Walsh diagram

Known shape of some AH2 molecules Molecular species No. of valence electrons 2 3 4 5 6 7 8 Shape

LiH2+ LiH2, BeH2+ BeH2, BH2+ BH2, AlH2, CH2+ CH2, SiH2, BH2-, NH2+ NH2, PH2, CH2-, OH2+ OH2, SH2, NH2-, FH2+

Bent Linear Linear Bent Bent Bent Bent

Recall: a molecule adopts the structure that best stabilises the HOMO. If the HOMO is unperturbed by the structural change under consideration, then the occupied MO lying closest to it governs the geometric preference.

Walsh diagram

OH2 vs SH2 vs SeH2? VSEPR? Decreased s/p hybridisation? (note bonding with pure p orbitals implies 90angles)

1a12 1b22 + BH2

2a11 131 CH2 NH2+ BH2AlH2 119 SiH2

2a12 110 115-120 102 93

2a12 1b11 NH2 OH2+ CH2PH2 AsH2 103 110.5 99 92 91

2a12 1b12 OH2 FH2+ NH2SH2 SeH2 TeH2 104.5 118 104 92.1 90.6 90

Dh

C2v

2 x sp hybrids + 2 x p lone pairs

3 x sp2 hybrids + 1 x p lone pair more p character in bonding orbitals

2nd order JT effect mixes s character (originally in 2g) into the lone pair (1u) so more p character accumulates in the bonding orbitals. Strength of 2nd order JT effect proportional to 1/E 2 factors to consider: Decrease in electronegativity destabilises u 3/4s orbitals of S/Se are lower than 2s of O (increased penetration) and also overlap more weakly with H 1s because they are diffuse. Both factors stabilise g both make 2nd order JT effect stronger in the heavier elements

PES revisited: origin of fine structure

PES revisited: origin of fine structure

PES revisited: HF

(0,0) band most intense

higher band most intense

narrow band

PES revisited: H2O (0,0) band most intense

The shapes of H3+ and H3-: 1st order JT effects, 3-centre-4-electron and 3-centre-2-electron bonds Consider MOs for the 2 limiting shapes for a 3-atom system: linear (Dh) and triangular (D3h)

D3h

(using the SALCS given in the handout)

The shapes of H3+ and H3-: 1st order JT effects, 3-centre-4-electron and 3-centre-2-electron bonds Consider MOs for the 2 limiting shapes for a 3-atom system: linear (Dh) and triangular (D3h)

Dh

Walsh diagram

increasing destructive overlap of terminal H 1s

increasing constructive overlap of terminal H 1s

Walsh diagram

(1st order) Jahn-Teller theorem If a non-linear molecule is in an orbitally degenerate state, it will distort to remove the degeneracy

orbitally degenerate therefore a first-order JT distortion

H3(a 3-centre-4-electron bond) c.f. hypervalent species such as HF2-, XeF2

H3+ (a 3-centre-2-electron bond) c.f. electron deficient species such as boranes

Bonding in Hypervalent Molecules XeF2 (hypervalent = 10 electrons on Xe) Possible explanations?

sp3d hybridisation?

Ionic resonance forms?

Bond order 0.5

Symmetry analysis (Dh)