Created by Zachary J. Tonzetich, University of Texas at San Antonio (zachary.tonzetich@utsa.edu) and posted on VIPEr (www.ionicviper.

org) on
4/23/2013, Copyright Tonzetich, 2013. This work is licensed under the Creative Commons Attribution, Non-Commercial, Share Alike License. To view a
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Molecular Orbital Theory for Organometallic Complexes: [Ti(8-C8H8)2]

Pentalene (Pn = C8H6, shown below) is an unsaturated hydrocarbon that is related to the
cyclopentadienyl (Cp) fragment by the edge-sharing ring-fusion of two C5H5 groups. In its doubly
charged form, C8H62, the pentalene dianion is capable of coordination to transition metals via its
system. Using the Hckel approach, we will first generate the MO diagram for the system of planar
C8H62 in D2h symmetry. We will then consider how the orbitals change upon bending of the fragment
about the central C-C bond (C2v). Finally, we will develop the qualitative MO diagram for the
sandwich complex, [Ti(8-C8H6)2].
To begin, let us consider the pentalene dianion in D2h symmetry with the following coordinate system:
x

1
8

+ 2e

3
7

(C2h)

(D2h)

Generating a representation for the 8 p orbitals in D2h symmetry gives:

D2h

E
8

C2(z)
0

C2(y)
-2

C2(x)
-2

i
0

(xy)
-8

(xz)
2

(yz)
2

Decomposing gives: = 2b2g + 2b3g + au + 3b1u

Descending to the pure rotational subgroup, D2 gives:
= 2b2 + 2b3 + a + 3b1
Applying the projection operator to each unique orbital (1, 2, and 3) generates the SALCs:
Pa(1) = (1)1 + (1)5 + (1)(5) + (1)(1) 0
Pa(2) = (1)2 + (1)6 + (1)(4) + (1)(8) 1 = 1/2(2 4 + 6 8)
Pa(3) = (1)3 + (1)7 + (1)(3) + (1)(7) 0
Pb1(1) = (1)1 + (1)5 + (1)(5) + (1)(1) 2 = 12(1 + 5)
Pb1(2) = (1)2 + (1)6 + (1)(4) + (1)(8) 3 = 1/2(2 + 4 + 6 + 8)
Pb1(3) = (1)3 + (1)7 + (1)(3) + (1)(7) 4 = 12(3 + 7)
Pb2(1) = (1)1 + (1)5 + (1)(5) + (1)(1) 5 = 12(1 5)
Pb2(2) = (1)2 + (1)6 + (1)(4) + (1)(8) 6 = 12(2 4 6 + 8)
Pb2(3) = (1)3 + (1)7 + (1)(3) + (1)(7) 0
Pb3(1) = (1)1 + (1)5 + (1)(5) + (1)(1) 0
Pb3(2) = (1)2 + (1)6 + (1)(4) + (1)(8) 7 = 12(2 + 4 6 8)
Pb3(3) = (1)3 + (1)7 + (1)(3) + (1)(7) 8 = 12(3 7)

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Created by Zachary J. Tonzetich, University of Texas at San Antonio (zachary.tonzetich@utsa.edu) and posted on VIPEr (www.ionicviper.org) on
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To determine the energies for each MO, we must solve the symmetry-factored secular determinant.
a
1
a
b1
b2
b3

b1

b2

H22 ES22

H23 ES23

H24 ES24

H32 ES32

H33 ES33

H34 ES34

H42 ES42

H43 ES43

H44 ES44

b3

H55 ES55

H56 ES56

H65 ES65

H66 ES66

H77 ES77

H78 ES78

H87 ES87

H88 ES88

H11 ES11

Solving for the Coulomb/resonance integrals and using the Hckel approximation (Hij = , , or 0;
Sij = ij) yields the following:
H11 =1||1= 14(H22 H24 + H26 H28 H42 + H86 + H88) = 14(4) =
H22 =2||2= 12(H11 + H15 + H51 + H55) = 12(2) =
H23 =2||3= (122)(H12 + H14 + H16 + H18 + H52 + H54 + H56 + H58) = (122)(4) = (22)
H24 =2||4= 12(H13 + H17 + H53 + H57) = 0
H32 =3||2= (122)(H21 + H25 + H41 + H45 + H61 + H65 + H81 + H85) = (122)(4) = (22)
H33 =3||3= 14(H22 + H24 + H26 + H28 + H42 + + H86 + H88) = 14(4) =
H34 =3||4= (122)(H23 + H27 + H43 + H47 + H63 + H67 + H83 + H87) = (122)(4) = (22)
H42 =4||2= 12(H31 + H35 + H71 + H75) = 0
H43 =4||3= (122)(H32 + H34 + H36 + H38 + H72 + H74 + H76 + H78) = (122)(4) = (22)
H44 =4||4= 12(H33 + H37 + H73 + H77) = 12( + + + ) = +
H55 =5||5= 12(H11 H15 H51 + H55) =
H56 =5||6= (122)(H12 H14 H16 + H18 H52 + H54 + H56 H58) = (122)(4) = (22)
H65 =6||5= (122)(H12 H14 H16 + H18 H52 + H54 + H56 H58) = (122)(4) = (22)
H66 =6||6= 14(H22 H24 H26 + H28 H42 + H86 + H88) = 14(4) =
H77 =7||7= 14(H22 + H24 H26 H28 + H42 + + H86 + H88) = 14(4) =
H78 =7||8= (122)(H23 H27 + H43 H47 H63 + H67 H83 + H87) = (122)(4) = (22)
H87 =8||7= (122)(H32 + H34 H36 H38 H72 H74 + H76 + H78) = (122)(4) = (22)
H88 =8||8= 12(H33 H37 H73 + H77) = 12( + ) =
1(a)

2(b1)

3(b1)

4(b1)

5(b2)

6(b2)

(2)

3(b1)

E
(2)

(2)

4(b1)

E
(2)

5(b2)

(2)

6(b2)

(2)

1(a)
2(b1)

8(b3)

E
(2)

(2)

+E

7(b3)
8(b3)

7(b3)

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Solving each square determinant gives the energies of each molecular orbital. Take note that we have
one 3 3 determinant, which is more difficult to solve than our normal 2 2 determinant (cannot use
the simple quadratic equation). Using any one of a variety of solver programs on the Internet, the
roots to the 3rd order polynomial can be easily determined. The final energies in units of are:

au: E(1) = 0
b1u: E(2, 3, 4) 2.343, 0.471, 1.814
b2g: E(5, 6) 1.414, 1.414
b3g: E(7, 8) , 2
Using these energies, the orbital coefficients are determined from the simultaneous equations that
give rise to the secular determinant (see appendix). Combining gives the forms of the MOs (colored
coded for phase):
1au(1) = 0.52 0.54 + 0.56 0.58
1b1u(2) = 0.2721 + 0.3182 + 0.4743 + 0.3184 + 0.2725 + 0.3186 + 0.4747 + 0.3188
2b1u(3) = 0.5121 + 0.1212 0.4573 + 0.1214 + 0.5125 + 0.1216 0.4577 + 0.1218
3b1u(4) = 0.4041 0.3672 + 0.2603 0.3674 + 0.4045 0.3676 + 0.2607 0.3678
1b2g(5) = 0.51 + 0.3542 0.3544 0.55 0.3546 + 0.3548
2b2g(6) = 0.51 0.3542 + 0.3544 0.55 + 0.3546 0.3548
1b3g(7) = 0.4082 + 0.4083 + 0.4084 0.4086 0.4087 0.4088
2b3g(8) = 0.2882 0.5773 + 0.2884 0.2886 + 0.5777 0.2888
We can now generate the MO diagram for the system of the pentalene dianion within the Hckel
approximation:

b3g
3bu
bg

Energy/


au

=0

bu
b3g

bg

bu

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Orbital pictures for occupied MOs

generated with Spartan at the
Hartree Fock level (6-311+G**).

Created by Zachary J. Tonzetich, University of Texas at San Antonio (zachary.tonzetich@utsa.edu) and posted on VIPEr (www.ionicviper.org) on
4/23/2013, Copyright Tonzetich, 2013. This work is licensed under the Creative Commons Attribution, Non-Commercial, Share Alike License. To view a
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Now let us consider folding of the C8 ring to give the bent pentalene dianion, which is the form that
binds to a single metal center. Within the Hckel approximation, I will roughly estimate the effect of
this folding by changing the value of certain resonance integrals (Hij) from to cos, where
represents the new angle between adjacent p orbitals (see Appendix). If we assume a bending angle
of 140 (estimated from X-ray data for other Ti pentalene compounds), the secular determinant will
change with new values for the resonance integrals describing interactions with orbitals 3 and 7:
H34 =3||4= (122)(H23 + H27 + H43 + H47 + H63 + H67 + H83 + H87) = (122)(4cos) = (22)cos
H43 =4||3= (122)(H32 + H34 + H36 + H38 + H72 + H74 + H76 + H78) = (122)(4cos) = (22)cos
H78 =7||8= (122)(H23 H27 + H43 H47 H63 + H67 H83 + H87) = (122)(4cos) = (22)cos
H87 =8||7= (122)(H32 + H34 H36 H38 H72 H74 + H76 + H78) = (122)(4cos) = (22)cos
1(a)

2(b1)

3(b1)

4(b1)

(2)

3(b1)

E
(2)

4(b1)

1(a)
2(b1)

5(b2)

6(b2)

E
(2)

(2)

7(b3)

8(b3)

E
(2)cos

(2)cos

E
E
(2)cos
(2)cos + E

5(b2)
6(b2)

7(b3)
8(b3)

Re-solving the determinants provides a new set of energies for the a1(b1u) and b1(b3g) symmetry MOs:
a1(b1u): E(2, 3, 4) 2.271, 0.498, 1.769
b1(b3g): E(7, 8) 0.920, 1.920
Are these energies conceptually reasonable? Yes, orbital 1a1(b1u) is destabilized upon bending because
it is fully bonding whereas orbitals 2a1 and 3a1 are stabilized because they possess antibonding
interactions between 2,4,6,8 and 3,7. The same logic holds for MOs 1b1 and 2b1. Incorporating these
results into a Walsh diagram (occupied MOs only) gives us the MO diagram for bent C8H62. Keep in
mind that the symmetry labels change as we move from D2h to C2v symmetry.
2

D2h

Energy/

=0

C2v

1au

1a2

2b1u

2a1
1b1

1b3g

1b2

1b2g
2

1a1

1b1u

4 of 7

Created by Zachary J. Tonzetich, University of Texas at San Antonio (zachary.tonzetich@utsa.edu) and posted on VIPEr (www.ionicviper.org) on
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Although no crystal structure exists, one proposed geometry of [Ti(C8H6)2] possesses staggered
pentalene ligands giving rise to overall D2d symmetry.

Ti

To determine the ligand group orbitals for a set of two bent pentalene dianions we take + and linear
combinations of each of the filled Hckel type orbitals shown above and consider their resulting
symmetries [note that in moving from C2v to D2d symmetry, the b1 and b2 orbitals must combine to give
an e set; use a correlation table!]. The resulting ligand group orbitals are shown below in an overhead
view along with their symmetries and matches to metal s, p, and d orbitals:

1a1 (s, dz2)

1b2 (pz, dxy)

1e (px,y)

2e (dxz,yz)

2a1 (s, dz2)

2b2 (pz, dxy)

1b1 (dx2-y2)

1a2

We are now ready to construct our MO diagram for [Ti(C8H6)2]. Since the two C8H62 ligands are
separated by several Angstroms, I will assume there is negligible interaction between the two ring
orbitals when giving rise to the ligand group orbitals (in other words, the MO of the form 1a + 1a is
of the same energy as 1a 1a ). We shall also convert from the Hckel energy scale ( and ) to eV.
To do so, I will use a value of ~2.6 eV for , and a value of ~7 eV for . The energies of the titanium
orbitals (3d, 4s, and 4p) can be approximated from the valence orbital ionization energies (VOIEs).
1

5 of 7

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4/23/2013, Copyright Tonzetich, 2013. This work is licensed under the Creative Commons Attribution, Non-Commercial, Share Alike License. To view a
copy of this license visit http://creativecommons.org/about/license/

[Ti(C8H6)2]
2
4e

pentalene

4a1

Ti

4b2
3e

-2

4p (b2 + e)

Energy (eV)

-4

3a1
2b1
3b2

-6

4s (a1)
1a2
1b1

b1 + a2
-8
-10
-12

2a1

a1 + b2

2b2
2e
2e

-14
-16

3d (a1 + b1 + b2 + e)

1e

a1 + b2

1b2

-18

1a1

Our diagram predicts a complex with 18 electrons occupying M-L bonding orbitals and a purely
ligand based non-bonding orbital (1a2). This diagram is reasonably consistent with both experimental
PES data, and calculations using much higher levels of theory (although the true geometry of
[Ti(8-C8H6)2] is believed to be other than purely D2d)!
Further Reading
1. Costuas, K.; Saillard, J.-Y. Is Ti(8-pentalene)2 a 20-electron complex? A theoretical investigation of a pseudo
electron-rich molecule. Chem. Commun. 1998, 2047-2048.
2. Gleiter, R.; Bethke, S.; Okubo, J.; Jonas, K. Electronic structure of bispentalene complexes of titanium,
zirconium, and hafnium: A photoelectron spectroscopic study. Organometallics 2001, 20, 4274-4278.
3. King, R. B. Chemical applications of topology and group theory: 37. Pentalene as a ligand in transition metal
sandwich complexes. Appl. Organomet. Chem. 2003, 17, 393-397.
4. Li, H.; Feng, H.; Sun, W.; Xie, Y.; King, R. B.; Schaefer, H. F. Mononuclear bis(pentalene) sandwich
compounds of the first-row transition metals: variable hapticity of the pentalene rings and intramolecular
coupling reactions. New J. Chem. 2011, 35, 1718-1729.

6 of 7

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Appendix
Example orbital coefficient calculation for b1u MOs (2, 3, 4):
The MOs will have the form: = c12 + c23+ c34
Secular equations describing theses MOs are: c1( E) + c2(2) = 0 AND c2(2) + c3( + E) = 0
Assigning the lowest of the three energies, E = + 2.343, to 2 gives:
c1( 2.343) + c2(1.414) = 0 c1 = (1.414c2)/(2.343) = 0.603c2
c2(1.414) + c3( + 2.343) = 0 c3 = (1.414c2)/(1.343) = 1.053c2
Applying the normalization condition: (0.603c2)2 + c22 + (1.053c2)2 = 1 c2 = 0.636; c1 = 0.383; c3 = 0.670
So we have: 2 = (0.383)2 + (0.636)3 + (0.670)4 = (0.271)(1 + 5) + (0.318)(2 + 4 + 6 + 8) + (0.474)(3 + 7)
Employing the other two energies for b1u will give coefficients for MOs 3 and 4. Similar logic can be applied
for MOs of other symmetry using the appropriate energies.

Description of from pentalene bending angle:

 

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