a) tetrahedral, sp3 b) square planar, sp2d c) trigonal pyramidal, sp3 d) bent, sp3 e) trigonal bipyramidal, sp3d f) octahedral, sp3d2

g) linear, sp h) trigonal planar, sp2

5.13 a) The hydrogen atoms are in the nodal plane of pz, so they experience zero net interaction. See Figure 5.17 for MO diagram. 5.14 a)

5.5

5.14 b) There is a small amount of N-H bonding character. See Figure 5.19 for MO diagram. 5.15 The orbitals will be the same as any other tetrahedron (Td CH4 see Figures 5.20 and 5.21) 5.16

b) I2 MO (See Figure 2.7, but with 5s and 5p) bond order = 1 I3+ MO (See Figure 5.15, but with 5s and 5p) bond order = 1 I3- MO (See Figure 5.30, ) bond order = 1/2 (delocalized bond over three atoms) This aggress with experimental evidence

I2 bond order = 1 I3+ bond order = 1 I3- bond order = 1/2

267 pm 268 pm 290 pm

5.17 a) BCl3 has D3h symmetry. 120o trigonal planar molecule (See Figure 5.23) s=a1 pz=a2 px and py=e
Cl Cl

Cl

Cl Cl

N Cl

5.17 b) NCl3 has C3v trigonal pyramidal, the Cl-N-Cl bonds are less then 120 (See Figure 5.19) s=a1 pz=a1 px and py=e

Problem 1 Each Cl has four valance orbitals (3s, 3px, 3py, and 3pz) generating a total of 16 LGOs (ligand group orbitals).
Chlorine 3s LGOs Chlorine 3px LGOs Chlorine 3py LGOs

A1g

A1g

A2g

B1g

B1g

B2g

Eu Chlorine 3pz LGOs

Eu Platinum 5d orbitals z2 A2u x2-y2 B 1g ( ) A1g

Eu Platinum 6p orbitals pz A2u

py Eu

px

B2u

xy

B2g

5s

A1g

Cl yz Eg Eg xz Cl Pt Cl Cl

y 2x z

D4h

The Cl 3s LGOs are too low in energy to effectively interact with the Pt valence orbitals. The Cl 3px, LGOs can form sigma bonds with Pt orbitals of the same symmetry (determined from D4h group table) ie the 6s, px, py and dx2-y2 The Cl 3 px, and py (Eu) LGOs have the correct symmetries to form bonds with the Pt orbitals of the same symmetry though these interactions will be weak since the orbitals are all run parallel to each other (and we all ready used the metal Eu set the 6px and 6py to make sigma bonds), while the B2g and Eg interactions from the dxz, yz and xy would be stronger since the lobes of these d-orbitals point towards the lobes of the

LGOs with the same symmetry. The Pt 6pz will interact to make a weaker bond (smaller spittining) compared to dxz, yz and xy orbitals. The A2g and B2u LGOs do not have the correct symmetry to interact with the s p or d orbitals of Pt so we will consider them non bonding LGOs. Bonding diagram using 4Cl LGOs and Pt valence orbitals (notice that orbitals only interact with orbitals of like symmetry). Figures on left shows all the interactions. Figure on right shows the strong type interactions.

Problem 2 O=SF4 is C2v with sigma bonds of symmetry = 3A1 + B1 + B2 corresponding to the 3s(A1), 3pz(A1), 3dz2(A1) and 3px(B1) and 3py (B2). While O=MoF4 is C4v with sigma bond of symmetry = 2A1, B1, E corresponding to the 5px and 5py (E) the 4dx2-y2 (B1) and any of the two of the three atomic orbitals with A1 symmetry the 5s 5pz or the 4dz2. The O=M bond can be formed using the upper lobes of the either the 4dxz or the 4dyz orbitals on Mo and the 3dxz or the 3dyz orbitals on S.