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Molybdenum(II) acetate

Names
Other names Dimolybdenum tetraacetate, tetra(aceto) dimolybdenum, Molybdenum(II) acetate dimer
Identifiers
CAS Number	14221-06-8
3D model (JSmol)	Interactive image
ChemSpider	76023
ECHA InfoCard	100.034.611
EC Number	238-089-5
PubChem CID	84269
CompTox Dashboard (EPA)	DTXSID90161972
InChI InChI=1S/4C2H4O2.2Mo/c4*1-2(3)4;;/h4*1H3,(H,3,4);;/q;;;;2*+2/p-4Key: DOOLFANBWPPEGQ-UHFFFAOYSA-J
SMILES 1234#(=C(C)O1)(=C(C)O2)(OC(C)=3)OC(C)=4
Properties
Chemical formula	C8H12Mo2O8
Molar mass	428.1010 g/mol
Appearance	Yellow solids
Boiling point	decomposes
Solubility in water	not soluble
Hazards
GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319
Precautionary statements	P222, P231, P235, P305+P351+P338, P422, P501
Safety data sheet (SDS)	External MSDS
Related compounds
Related compounds	Copper(II) acetate Chromium(II) acetate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Y verify (what is  ?) Infobox references

Molybdenum(II) acetate is a coordination compound with the formula Mo₂(O₂CCH₃)₄. It is a yellow, diamagnetic, air-stable solid that is slightly soluble in organic solvents. Molybdenum(II) acetate is an iconic example of a compound with a metal-metal quadruple bond.

Structure

Like several other transition metal carboxylate complexes, Mo₂(O₂CCH₃)₄ adopts a Chinese lantern structure. Each Mo(II) center in Mo₂(O₂CCH₃)₄ has four d valence electrons. These eight d-electrons form one σ, two π bonds, and one δ bond, creating a bonding electron configuration of σπδ. Each of these bonds are formed by the overlapping of pairs of d orbitals. The four acetate groups bridge the two metal centers. The Mo-O bond between each Mo(II) center and O atom from acetate has a distance of 2.119 Å, and the Mo-Mo distance between the two metal centers is 2.0934 Å.

Preparation

Mo₂(O₂CCH₃)₄ is prepared by treating molybdenum hexacarbonyl (Mo(CO)₆) with acetic acid. The process strips CO ligands from the hexacarbonyl and results in the oxidation of Mo(0) to Mo(II).

2 Mo(CO)₆ + 4 HO₂CCH₃ → Mo₂(O₂CCH₃)₄ + 12 CO + 2 H₂

Trinuclear clusters are byproducts.

The reaction of HO₂CCH₃ and Mo(CO)₆ was first investigated by Bannister et al. in 1960. At the time, quadruple metal-metal bonds had not yet been discovered, so these authors proposed that Mo(O₂CCH₃)₂ was tetrahedral. This perspective changed with Mason's characterization.

Applications

Mo₂(O₂CCH₃)₄ is generally used as an intermediate compound in a process to form other quadruply bonded molybdenum compounds. The acetate ligands can be replaced to give new compounds such as and Mo₂Cl₄₄.

References

1. "Molybdenum (CAS Number 14221-06-8) : Strem Product Catalog". www.strem.com. Retrieved 27 December 2021.
2. ^ Girolami, G. S.; Rauchfuss, T. B. and Angelici, R. J., "Synthesis and Technique in Inorganic Chemistry third edition", University Science Books: Mill Valley, CA, 1999, ISBN 0-935702-48-2
3. Cotton, F. A.; Hillard, E.A.; Murillo, C. A.; Zhou, H.-C. "After 155 Years, A Crystalline Chromium Carboxylate with a Supershort Cr-Cr Bond" J. Am. Chem. Soc., 2000, 122, 416-417. doi:10.1021/ja993755i.
4. Blaudeau, J. P.; Pitzer, R. M. “ Ab Initio Studies of Ligand Effects on the Metal-Metal Bond in Dimolybdenum Complexes” J.Phys. Chem. 1994, vol. 98, pp. 4575-4579.
5. Brignole, A.G.; Cotton, F.A., “Rhenium and Molybdenum compounds containing quadruple compounds” Inorg. Synth. 1972, volume 13, pp. 81-89. doi:10.1002/9780470132449.ch15
6. Pence, L. E.; Weisgerber, A. M.; Maounis, F.A.; “Synthesis of Molybdenum-Molybdenum Quadruple Bonds” J. Chem. Educ., 1999, vol. 76, 404-405.
7. Bino, A.; Cotton, F.A.; Dori, A.; J. Am. Chem. Soc. 1981, vol. 103, pp. 243-244. “A Aqueous New Chemistry of Organometallic, Trinuclear Cluster Compounds of Molybdenum”.
8. Bannister, E.; Wikinson, G. “Molybdenum(II) carboxylates” Chem. Ind. 1960, 319.
9. Stephenson, T.A.; Bannister, E.; Wilkinson, G. “Molybdenum(II) Carboxylates” J. Chem. Soc., 1964, pp. 2538. doi:10.1039/JR9640002538
10. D. Lawton, R. Mason "The Molecular Structure of Molybdenum(II) Acetate"J. Am. Chem. Soc. 1965, vol 87, pp 921–922. doi:10.1021/ja01082a046
11. Tsai, Y.C.; Chen H.Z.; Chang, C.C.; Yu, J.K.; Lee, G.H.; Wang, Y.; Kuo, T.S. “Journey from Mo-Mo Quadruple Bonds to Quintuple Bonds” J. Am. Chem. Soc., 2009, 131, 12534-12535. doi:10.1021/ja905035f
12. Handa, M.; Mikuriya, M.; Kotera, T.; Yamada, K.; Nakso, T.; Matsumoto, H.; Kasuga, K. “Linear Chain Compounds of Molybdenum(II) Acetate Linked by Pyazine, 4,4’-Bipyridine, and 1,4- Diazabicyclooctane” Bull. Chem. Soc. Jpn., 1995,68, 2567-2572.

• Acetates
• Molybdenum(II) compounds