s4s4 c3c3 s6s6. p z, (d xz, d yz ) s a’ 1 (p x, p y ): e’ p z : a” 2 (d x2 – y2, d xy ):...
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![Page 1: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/1.jpg)
S4
C3
S6
![Page 2: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/2.jpg)
H2N
Si
NH2
NH2
H2N
Si
NH2
NH2
etc.
![Page 3: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/3.jpg)
pz, (dxz, dyz)
s A’1(px , py): E’pz: A”2
(dx2 – y2, dxy): E’(dxz, dyz): E’’dz2: A’1
![Page 4: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/4.jpg)
3 0 -1 -3 0 1
![Page 5: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/5.jpg)
f) Now shift to the C3vpoint group and obtain the irreducible reps to which the pi bonding NH2 unit orbitals belong.
E 2C3 3v
3 0 1
= A1 + E
![Page 6: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/6.jpg)
^^
RRh
lP
jj
jj
A1
E1 E2
![Page 7: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/7.jpg)
A1
E1 E2
On going from C3v to D3h maintain same behavior for the C3v operations (E, C3 and v). Thus A1 in C3v could be either A’1 or A’’2. Choose A2’’ since it is antisym for h.Likewise, E could be either E’ or E’’ Choose E’’ since it is antisym for h.Thus A”2 and E’
![Page 8: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/8.jpg)
A2”
E” (1)E” (2)
Si Orbitalss A’1(px , py): E’Pz: A”2
(x2 – y2, xy): E’(xz, yz): E’’z2: A’1
i) Show bonding between the Si orbitals and the symmetry adapted NH2 orbitals
![Page 9: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/9.jpg)
![Page 10: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/10.jpg)
![Page 11: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/11.jpg)
![Page 12: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/12.jpg)
i x,z
E C2(y)
C2(y)
x,z i = C2(y)
![Page 13: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/13.jpg)
i
E C2(y)
C2’(-xy)xy,z
C2’(-xy)
![Page 14: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/14.jpg)
x,z
E C2(y)
C4 (z)xy,z
C2’(-xy)
C4 (z) C2 (z)
![Page 15: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/15.jpg)
E C2(y)
xy,z
C2’(-xy)
C4 (z) C2 (z)
C2 (z)
xy,z
xy,z
![Page 16: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/16.jpg)
E C2(y)
C2’(-xy)
C4 (z)
C2 (z)
h
xy,z
h
xy,z
C2’(-xy)
D4h
![Page 17: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/17.jpg)
Coordination number 1
Very rare, bulky ligands, linear structures, no possible isomers
![Page 18: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/18.jpg)
Coordination number 2
Also rare, typical of d10, linear structures, no possible isomers
![Page 19: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/19.jpg)
Coordination number 3
Also typical of d10, trigonal planar structures (rarely T-shaped), no possible isomers
![Page 20: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/20.jpg)
Coordination number 4
L4
L1
M
L3
L2
L2
M
L1 L2
L1
L1
M
L1 L2
L2
cis
transTetrahedral(2 enantiomers if all ligands different)
Square planar(2 geometrical isomer
for two types of ligands)typical of d8
Very common
![Page 21: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/21.jpg)
Tetrahedral
Square planar
![Page 22: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/22.jpg)
Coordination number 5
Trigonal bipyramidal (tbp) Square-based pyramidal sbp)
Very similar energies, they may easily interconvert in solution (fluxionality)
Le M
Le
Le
La
La
Lb
MLb Lb
Lb
La
![Page 23: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/23.jpg)
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Coordination number 6
M
Octahedralmost common
Trigonal prismless common
![Page 25: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/25.jpg)
Some possible isomers in octahedral complexes
B
M
A B
B
A
B
B
M
B B
B
A
A
cis-MA2B4 trans-MA2B4
B
MB A
A
A
B
B
MB B
A
A
A
fac-MA3B3 mer-MA3B3
![Page 26: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/26.jpg)
Some examples of trigonal prismatic structures
![Page 27: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/27.jpg)
Coordination number 7
M M
Pentagonal bipyramidal
Capped octahedral Cappedtrigonal prismatic
M
![Page 28: S4S4 C3C3 S6S6. p z, (d xz, d yz ) s A’ 1 (p x, p y ): E’ p z : A” 2 (d x2 – y2, d xy ): E’ (d xz, d yz ): E’’ d z2 : A’ 1](https://reader030.vdocuments.mx/reader030/viewer/2022032521/56649d5a5503460f94a3a27d/html5/thumbnails/28.jpg)
Examples of coordination number 7