Molybdenum(II) acetate

Last updated
Molybdenum(II) acetate
Mo2(OAc)4.svg
Names
Other names
Dimolybdenum tetraacetate,
tetra(aceto) dimolybdenum,
Molybdenum(II) acetate dimer
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.034.611 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 238-089-5
PubChem CID
  • InChI=1S/4C2H4O2.2Mo/c4*1-2(3)4;;/h4*1H3,(H,3,4);;/q;;;;2*+2/p-4 Yes check.svgY
    Key: DOOLFANBWPPEGQ-UHFFFAOYSA-J Yes check.svgY
  • [Mo-2]1234#[Mo-2]([O+]=C(C)O1)([O+]=C(C)O2)(OC(C)=[O+]3)OC(C)=[O+]4
Properties
C8H12Mo2O8
Molar mass 428.1010 g/mol
AppearanceYellow solids
Boiling point decomposes
not soluble
Hazards
GHS labelling: [1]
GHS-pictogram-exclam.svg
Warning
H315, H319
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 [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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. [2]

Contents

Structure

Like several other transition metal carboxylate complexes, Mo2(O2CCH3)4 adopts a Chinese lantern structure. [3] 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 σ2π4δ2. Each of these bonds are formed by the overlapping of pairs of d orbitals. [4] 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). [5] [6]

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

Trinuclear clusters are byproducts. [7]

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. [8] [9] This perspective changed with Mason's characterization. [10]

Applications

Mo2(O2CCH3)4 is generally used as an intermediate compound in a process to form other quadruply bonded molybdenum compounds. [2] The acetate ligands can be replaced to give new compounds such as [Mo2Cl8]4− and Mo2Cl4[P(C4H9)3]4. [2] [11] [12]

Related Research Articles

<span class="mw-page-title-main">Metallocene</span> Type of compound having a metal center

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

In organic chemistry, a carbyne is a general term for any compound whose structure consists of an electrically neutral carbon atom connected by a single covalent bond and has three non-bonded electrons. The carbon atom has either one or three unpaired electrons, depending on its excitation state; making it a radical. The chemical formula can be written R−C· or R−C, or just CH.

<span class="mw-page-title-main">Alkyne metathesis</span>

Alkyne metathesis is an organic reaction that entails the redistribution of alkyne chemical bonds. The reaction requires metal catalysts. Mechanistic studies show that the conversion proceeds via the intermediacy of metal alkylidyne complexes. The reaction is related to olefin metathesis.

<span class="mw-page-title-main">Molybdenum hexacarbonyl</span> Chemical compound

Molybdenum hexacarbonyl (also called molybdenum carbonyl) is the chemical compound with the formula Mo(CO)6. This colorless solid, like its chromium, tungsten, and seaborgium analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero oxidation state.

<span class="mw-page-title-main">Ditungsten tetra(hpp)</span> Chemical compound

Tetrakis(hexahydropyrimidinopyrimidine)ditungsten(II), known as ditungsten tetra(hpp), is the name of the coordination compound with the formula W2(hpp)4. This material consists of a pair of tungsten centers linked by the conjugate base of four hexahydropyrimidopyrimidine (hpp) ligands. It adopts a structure sometimes called a Chinese lantern structure or paddlewheel compound, the prototype being copper(II) acetate.

<span class="mw-page-title-main">Palladium(II) acetate</span> Chemical compound

Palladium(II) acetate is a chemical compound of palladium described by the formula [Pd(O2CCH3)2]n, abbreviated [Pd(OAc)2]n. It is more reactive than the analogous platinum compound. Depending on the value of n, the compound is soluble in many organic solvents and is commonly used as a catalyst for organic reactions.

<span class="mw-page-title-main">Quintuple bond</span> Chemical bond involving ten bonding electrons

A quintuple bond in chemistry is an unusual type of chemical bond, first reported in 2005 for a dichromium compound. Single bonds, double bonds, and triple bonds are commonplace in chemistry. Quadruple bonds are rarer and are currently known only among the transition metals, especially for Cr, Mo, W, and Re, e.g. [Mo2Cl8]4− and [Re2Cl8]2−. In a quintuple bond, ten electrons participate in bonding between the two metal centers, allocated as σ2π4δ4.

<span class="mw-page-title-main">Chromium(II) acetate</span> Chemical compound

Chromium(II) acetate hydrate, also known as chromous acetate, is the coordination compound with the formula Cr2(CH3CO2)4(H2O)2. This formula is commonly abbreviated Cr2(OAc)4(H2O)2. This red-coloured compound features a quadruple bond. The preparation of chromous acetate once was a standard test of the synthetic skills of students due to its sensitivity to air and the dramatic colour changes that accompany its oxidation. It exists as the dihydrate and the anhydrous forms.

<span class="mw-page-title-main">Quadruple bond</span> Chemical bond involving eight electrons; has one sigma, two pi, and one delta bond

A quadruple bond is a type of chemical bond between two atoms involving eight electrons. This bond is an extension of the more familiar types of covalent bonds: double bonds and triple bonds. Stable quadruple bonds are most common among the transition metals in the middle of the d-block, such as rhenium, tungsten, technetium, molybdenum and chromium. Typically the ligands that support quadruple bonds are π-donors, not π-acceptors. Quadruple bonds are rare as compared to double bonds and triple bonds, but hundreds of compounds with such bonds have been prepared.

<span class="mw-page-title-main">Bridging ligand</span> Ligand which connects two or more (usually metal) atoms in a coordination complex

In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually restricted to small ligands such as pseudohalides or to ligands that are specifically designed to link two metals.

<span class="mw-page-title-main">Cyclopentadienylmolybdenum tricarbonyl dimer</span> Chemical compound

Cyclopentadienylmolybdenum tricarbonyl dimer is the chemical compound with the formula Cp2Mo2(CO)6, where Cp is C5H5. A dark red solid, it has been the subject of much research although it has no practical uses.

<span class="mw-page-title-main">Sextuple bond</span> Covalent bond involving 12 bonding electrons

A sextuple bond is a type of covalent bond involving 12 bonding electrons and in which the bond order is 6. The only known molecules with true sextuple bonds are the diatomic dimolybdenum (Mo2) and ditungsten (W2), which exist in the gaseous phase and have boiling points of 4,639 °C (8,382 °F) and 5,930 °C (10,710 °F) respectively.

<span class="mw-page-title-main">Potassium octachlorodimolybdate</span> Chemical compound

Potassium octachlorodimolybdate is an inorganic compound with the chemical formula K4[Mo2Cl8]. It is known as a red-coloured, microcrystalline solid. The anion is of historic interest as one of the earliest illustrations of a quadruple bonding. The salt is usually obtained as the pink-coloured dihydrate.

<span class="mw-page-title-main">Organomolybdenum chemistry</span> Chemistry of compounds with Mo-C bonds

Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common.

<span class="mw-page-title-main">(Mesitylene)molybdenum tricarbonyl</span> Chemical compound

(Mesitylene)molybdenum tricarbonyl is an organomolybdenum compound derived from the aromatic compound mesitylene (1,3,5-trimethylbenzene) and molybdenum carbonyl. It exists as pale yellow crystals, which are soluble in organic solvents but decompose when in solution. It has been examined as a catalyst and reagent.

<span class="mw-page-title-main">Potassium octachlorodirhenate</span> Chemical compound

Potassium octachlorodirhenate(III) is an inorganic compound with the formula K2Re2Cl8. This dark blue salt is well known as an early example of a compound featuring quadruple bond between its metal centers. Although the compound has no practical value, its characterization was significant in opening a new field of research into complexes with quadruple bonds.

<span class="mw-page-title-main">Transition metal nitrile complexes</span> Class of coordination compounds containing nitrile ligands (coordinating via N)

Transition metal nitrile complexes are coordination compounds containing nitrile ligands. Because nitriles are weakly basic, the nitrile ligands in these complexes are often labile.

<span class="mw-page-title-main">Transition metal imido complex</span>

In coordination chemistry and organometallic chemistry, transition metal imido complexes is a coordination compound containing an imido ligand. Imido ligands can be terminal or bridging ligands. The parent imido ligand has the formula NH, but most imido ligands have alkyl or aryl groups in place of H. The imido ligand is generally viewed as a dianion, akin to oxide.

<span class="mw-page-title-main">Metal cluster compound</span> Cluster of three or more metals

Metal cluster compounds are a molecular ion or neutral compound composed of three or more metals and featuring significant metal-metal interactions.

<span class="mw-page-title-main">Transition metal carboxylate complex</span> Class of chemical compounds

Transition metal carboxylate complexes are coordination complexes with carboxylate (RCO2) ligands. Reflecting the diversity of carboxylic acids, the inventory of metal carboxylates is large. Many are useful commercially, and many have attracted intense scholarly scrutiny. Carboxylates exhibit a variety of coordination modes, most common are κ1- (O-monodentate), κ2 (O,O-bidentate), and bridging.

References

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  2. 1 2 3 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- Diazabicyclo[2.2.2]octane” Bull. Chem. Soc. Jpn., 1995,68, 2567-2572.