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Cyclopentadienylmolybdenum tricarbonyl dimer: Difference between revisions

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{{chembox
{{chembox
| Watchedfields = changed
| verifiedrevid = 385818390
| verifiedrevid = 427297729
⚫
| ImageFile = Cp2Mo2(CO)6.png
| ImageFile1 = CP2Mo2(CO)6imp.svg
| ImageSize = 150px
⚫
| ImageFile2 = Cp2Mo2(CO)6+spatula.jpg
| IUPACName = bis(tricarbonyl[η<sup>5</sup>-cyclopentadienyl]<br />molybdenum)(''Mo''—''Mo'')
| OtherNames = cyclopentadienyl molybdenum
| IUPACName = bis(tricarbonyl[η<sup>5</sup>-cyclopentadienyl]<wbr />molybdenum)(''Mo''—''Mo'')
| OtherNames = cyclopentadienyl molybdenum
carbonyl dimer<br />Bis(tricarbonylcyclopentadienylmolybdenum)
carbonyl dimer<br />Bis(tricarbonylcyclopentadienylmolybdenum)
| Section1 = {{Chembox Identifiers
|Section1={{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|??}}
| CASNo = 12091-64-4
| CASNo = 12091-64-4
| RTECS =
| PubChem = 11113722
| ChemSpiderID = 21241602
| EINECS = 235-156-0
| StdInChI=1S/2C5H5.6CO.2Mo/c2*1-2-4-5-3-1;6*1-2;;/h2*1-5H;;;;;;;;
| StdInChIKey = XCUPBPUEWLTPMQ-UHFFFAOYSA-N
| SMILES = [C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].C1=C[CH]C=C1.C1=C[CH]C=C1.[Mo].[Mo]
}}
}}
| Section2 = {{Chembox Properties
|Section2={{Chembox Properties
| Formula = Mo<sub>2</sub>(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(CO)<sub>6</sub></sub></sub>
| Formula = Mo<sub>2</sub>(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(CO)<sub>6</sub>
| MolarMass = 489.96 g/mol
| C=16 | H=10 | O=6 | Mo=2
| Appearance = dark red crystalline solid
| Appearance = dark red crystalline solid
| Solubility = insoluble
| Solubility = insoluble
| Solvent = other solvents
| Solvent = other solvents
| SolubleOther =
| SolubleOther =
| MeltingPt = 222 °C
| MeltingPtC = 222
| BoilingPt = dec.
| BoilingPt = dec.
}}
}}
| Section3 = {{Chembox Structure
|Section3={{Chembox Structure
| Coordination =
| Coordination =
| CrystalStruct = monoclinic
| CrystalStruct = monoclinic
| Dipole = 0.112 [[Debye|D]]
| Dipole = 0.112 [[Debye|D]]
}}
}}
| Section7 = {{Chembox Hazards
|Section7={{Chembox Hazards
| ExternalMSDS =
| ExternalSDS =
| MainHazards = flammable
| MainHazards = flammable
| FlashPt =
| FlashPt =
| GHSPictograms = {{GHS06}}{{GHS07}}
| RPhrases = 20/21/22
| SPhrases = 36
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|302|312|332}}
| PPhrases = {{P-phrases|}}
}}
}}
| Section8 = {{Chembox Related
|Section8={{Chembox Related
| Function = compounds
| OtherFunction_label = compounds
| OtherFunctn = (η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>4</sub>
| OtherFunction = (η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>4</sub>
}}
}}
}}
}}


'''Cyclopentadienylmolybdenum tricarbonyl dimer''' is the [[chemical compound]] with the formula Cp<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub>, where Cp is C<sub>5</sub>H<sub>5</sub>. This a dark red [[crystal]]line solid is air stable in solid form, but decomposes in solution when exposed to air. It is one of the most important and most accessible organomolybdenum compounds, although it has no practical uses.
'''Cyclopentadienylmolybdenum tricarbonyl dimer''' is the [[chemical compound]] with the formula Cp<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub>, where Cp is C<sub>5</sub>H<sub>5</sub>. A dark red solid, it has been the subject of much research although it has no practical uses.


==Structure and synthesis==
==Structure and synthesis==
The molecule exists in two [[rotamer]]s, gauche and anti.<ref>{{cite web | author = Brian Mann | url = http://brian-mann.staff.shef.ac.uk/Cp2Mo2CO6.html | title = Fluxionality of Cp<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub> | publisher = [[University of Sheffield]] |date=1997-01-06}}</ref> The six CO ligands are terminal and the Mo-Mo bond distance is 3.2325 Å.<ref>{{cite journal | author = R. D. Adams, D. M. Collins, and [[F. A. Cotton]] | title = Molecular Structures and Barriers to Internal Rotation in Bis(&eta;5 -cyclopentadienyl)hexacarbonylditungsten and Its Molybdenum Analog | journal = [[Inorg. Chem.]] | year = 1974 | volume = 13 | pages = 1086–1090 | doi = 10.1021/ic50135a015 | issue = 5}}</ref> The compound is prepared by treatment of [[Molybdenum hexacarbonyl|Mo(CO)<sub>6</sub>]] in hot [[dicyclopentadiene]]. A high-yield route to the [[Dimer (chemistry)|dimer]] involves a two-step, one-pot [[chemical synthesis|synthesis]].<ref>{{cite journal | author = M. David Curtis, Michael S. Hay | year = 1990 | title = Cyclopentadienyl Metal Carbonyl Dimers of Molybdenum and Tungsten | journal = [[Inorganic Syntheses]] | volume = 28 | pages = 150–152 | isbn = 9780471526193 | doi = 10.1002/9780470132593.ch40 | publisher = J. Wiley & Sons | location = New York}}</ref> In the first step Mo(CO)<sub>6</sub> is converted in hot [[Acetonitrile|CH<sub>3</sub>CN]] to the [[air-sensitive]] Mo(CO)<sub>3</sub>(CH<sub>3</sub>CN)<sub>3</sub>.
The molecule exists in two [[rotamer]]s, gauche and anti.<ref>{{cite web | author = Brian Mann | url = http://brian-mann.staff.shef.ac.uk/Cp2Mo2CO6.html | title = Fluxionality of Cp<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub> | publisher = [[University of Sheffield]] |date=1997-01-06}}</ref> The six CO ligands are terminal and the Mo-Mo bond distance is 3.2325 Å.<ref>{{cite journal | author = R. D. Adams, D. M. Collins, and [[F. A. Cotton]] | title = Molecular Structures and Barriers to Internal Rotation in Bis(η5-cyclopentadienyl)hexacarbonylditungsten and Its Molybdenum Analog | journal = [[Inorg. Chem.]] | year = 1974 | volume = 13 | pages = 1086–1090 | doi = 10.1021/ic50135a015 | issue = 5| doi-access = free }}</ref> The compound is prepared by treatment of [[molybdenum hexacarbonyl]] with [[sodium cyclopentadienide]] followed by oxidation of the resulting NaMo(CO)<sub>3</sub>(C<sub>5</sub>H<sub>5</sub>).<ref>{{cite journal |first1=A. R.|last1= Manning|first2=Paul|last2=Hacket |first3=Ralph|last3=Birdwhistell| year = 1990 | title = Hexacarbonylbis(η<sup>5</sup>-Cyclopentadienyl)Dichromium, Molybdenum, and Tungsten and their Analogs, M<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>R)<sub>2</sub>(CO)<sub>6</sub> (M = Cr, Mo, and W; R = H, Me or PhCH<sub>2</sub>) | journal = [[Inorganic Syntheses]] | volume = 28 | pages = 148–149 | doi = 10.1002/9780470132593.ch39|isbn= 9780470132593}}</ref> Other methods have been developed starting with Mo(CO)<sub>3</sub>(CH<sub>3</sub>CN)<sub>3</sub> instead of Mo(CO)<sub>6</sub>.<ref name=MDC>{{cite book |first1=M. David|last1= Curtis |first2=Michael S.|last2=Hay |title= Inorganic Syntheses | year = 1990 | chapter = Cyclopentadienyl Metal Carbonyl Dimers of Molybdenum and Tungsten | series = Inorganic Syntheses | volume = 28 | pages = 150–152 | doi = 10.1002/9780470132593.ch40 |isbn= 9780470132593 }}</ref>
:Mo(CO)<sub>6</sub> + 3 CH<sub>3</sub>CN → Mo(CO)<sub>3</sub>(CH<sub>3</sub>CN)<sub>3</sub> + 3 CO
:2 Mo(CO)<sub>3</sub>(CH<sub>3</sub>CN)<sub>3</sub> + 2 C<sub>5</sub>H<sub>6</sub> → (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub> + H<sub>2</sub> + 6 CH<sub>3</sub>CN


==Reactions==
==Reactions==
Thermolysis of this compound in hot solution of [[diglyme]] (bis(2-methoxyethyl)ether) results in decarbonylation, giving the tetracarbonyl, which has a formal triple bond between the Mo centers (''d''<sub>MoMo</sub> = 2.448 Å):<ref>Cotton, F. A.; Walton, R. A. “Multiple Bonds Between Metal Atoms” Oxford (Oxford): 1993, p 564ff. ISBN 0-19-855649-7.</ref>
[[Thermal decomposition|Thermolysis]] of this compound in hot solution of [[diglyme]] (bis(2-methoxyethyl)ether) results in decarbonylation, giving the tetracarbonyl,<ref name=MDC/> which has a formal triple bond between the Mo centers (''d''<sub>MoMo</sub> = 2.448 Å):<ref>Cotton, F. A.; Walton, R. A. "Multiple Bonds Between Metal Atoms" Oxford (Oxford): 1993, p 564ff. {{ISBN|0-19-855649-7}}.</ref>
:(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub> → (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>4</sub> + 2 CO
:(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>6</sub> → (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>Mo<sub>2</sub>(CO)<sub>4</sub> + 2 CO
The resulting cyclopentadienylmolybdenum dicarbonyl dimer in turn binds a variety of substrates across the metal-metal triple bond.
The resulting cyclopentadienylmolybdenum dicarbonyl dimer in turn binds a variety of substrates across the metal-metal triple bond.


==Related compounds==
* [[Cyclopentadienyltungsten tricarbonyl dimer]]
* [[Cyclopentadienylchromium tricarbonyl dimer]]
==References==
==References==
<references/>
<references/>
{{molybdenum compounds}}

{{Cyclopentadienide complexes}}
[[Category:Organomolybdenum compounds]]
[[Category:Organomolybdenum compounds]]
[[Category:Carbonyl complexes]]
[[Category:Carbonyl complexes]]
[[Category:Dimers (chemistry)]]

[[Category:Half sandwich compounds]]
[[ja:トリカルボニルシクロペンタジエニルモリブデンダイマー]]
[[Category:Cyclopentadienyl complexes]]
[[Category:Chemical compounds containing metal–metal bonds]]
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