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Tutorial 1

The document is a tutorial for CHEM4341/6115 focusing on metal-metal bonds, specifically comparing Mo2(OAc)4, Ru2(OAc)4, and Cu2(OAc)4. It includes questions about the effects of geometry and non-axial ligands on M-M bond lengths, as well as structural differences in diiron complexes. Additionally, it provides synthetic questions related to the preparation of specific compounds and references relevant literature.

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4 views14 pages

Tutorial 1

The document is a tutorial for CHEM4341/6115 focusing on metal-metal bonds, specifically comparing Mo2(OAc)4, Ru2(OAc)4, and Cu2(OAc)4. It includes questions about the effects of geometry and non-axial ligands on M-M bond lengths, as well as structural differences in diiron complexes. Additionally, it provides synthetic questions related to the preparation of specific compounds and references relevant literature.

Uploaded by

chanelwyn
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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CHEM4341/6115 Tutorial 1

Metal-Metal Bonds
Prof. Chi-Ming Che
Date: 17 Oct 2024
12:30 – 13:30
Zoom
• Compare and explain the structural differences between Mo2(OAc)4,
Ru2(OAc)4 and Cu2(OAc)4

O O
H O O H
O Cu Cu O
H O O H
O O

Mo2(OAc)4 Rh2(OAc)4 Cu2(OAc)4


d4-d4 d7-d7 d9-d9
• For d9-d9 dinuclear systems, does the geometry affect the M-M bond order?

Harisomayajula, N. S., Nair, A. K., & Tsai, Y. C.


(2014). Chemical Communications, 50(26), 3391-3412.
• How does non-axial ligands affect the M-M bond length in dinuclear
system?
Non axial ligand has minimal effect
on M-M bond length:
- Electronic effect
- Steric effect

1: 2: 3: 4:
R = H, Ar = 2,4,6-Me3C6H2 R = H, Ar = 2,6-Et2C6H3 R = H, Ar = 2,6-iPr2C6H3 R = Me, Ar = 2,6-iPr2C6H3
Cr-Cr = 1.7404(8) Å Cr-Cr = 1.7454(1) Å Cr-Cr = 1.7472(10) Å Cr-Cr = 1.7395(7) Å

Harisomayajula, N. S., Nair, A. K., & Tsai, Y. C.


(2014). Chemical Communications, 50(26), 3391-3412.
• Additional Questions

• Why are there very few examples of d9-d9 metal-metal single bond for
first row transition metals?
Q1: Account for the shift of   * absorption
Study Question 1 band

(nBu4N)2[Re2Br8]
(nBu4N)2[Re2Cl8]

The diminished intensity of a band attributable to the William C. Trogler, Harry B. Gray, Acc. Chem. Res., 1978,
  * transition is a consequence of poor orbital overlap. 11, 6, 232-239
Study question 1(cont.)
(TBA)2(Re2Cl8)  ~ 690 nm
(TBA)2(Re2Br8)  ~ 750 nm

Comparing photon energy:

1/690 vs 1/750

Consider Cl- vs Br-


- Atomic size
- Electronegativity
- Bond distance
Study Question 2
3D structure of H2OEP

3D structure of H2TMP

Sterically hindered ligand


Study Question 2 (Cont.)
Study Question 3

Q: Account for the structural difference between the two diiron complexes
Study Question 3
• Correlate with metallic bonding (see lecture notes)
• 3d orbitals vs 4d/ 5d orbitals
• Weaker stabilization and destabilization of orbitals
• Properties of the ligands
Synthetic questions
• Suggest how the following can be prepared
• Potassium octabromodirhenate
• [(TPP)Mo=Re(OEP)]PF6

F. A. Cotton, N. F. Curtis, B. F. G. Johnson, W. R. Robinson, Inorg. Chem. 1965, 4, 326.


J. P. Collman, R. Boulatov, G. B. Jameson, Angew. Chem. Int. Ed. 2001, 40, 1271.
• Suggest how the following can be prepared
• Potassium octabromodirhenate
Re(VII), d0 Re(III), d4
[ReO4]- + HBr + H3PO2 [Re2Br8]2-
• [(TPP)Mo=Re(OEP)]PF6

F. A. Cotton, N. F. Curtis, B. F. G. Johnson,


W. R. Robinson, Inorg. Chem. 1965, 4, 326.

J. P. Collman, R. Boulatov, G. B. Jameson,


Angew. Chem. Int. Ed. 2001, 40, 1271.
Q&A Section

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