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⚫ | '''Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate''' is an [[organoruthenium compound]] with the formula [(C<sub>5</sub>H<sub>5</sub>)Ru(NCCH<sub>3</sub>)<sub>3</sub>]PF<sub>6</sub> |
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| Formula = C11H14N3RuPF6 |
| Formula = C11H14N3RuPF6 |
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| MolarMass = 434.28 |
| MolarMass = 434.28 |
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| Appearance = yellow/brown |
| Appearance = yellow/brown solid |
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| Density = |
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| Melting Pt = |
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⚫ | '''Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate''' is an [[organoruthenium compound]] with the formula [(C<sub>5</sub>H<sub>5</sub>)Ru(NCCH<sub>3</sub>)<sub>3</sub>]PF<sub>6</sub>, abbreviated [CpRu(NCMe)<sub>3</sub>]PF<sub>6</sub>. It is a is a yellow-brown solid that is soluble in polar organic solvents. The compound provides access to effectively RuCp<sup>+</sup> for further derivitization.<ref name=Mann>Gill, Thomas P; Mann, Kent R (1982) “Photochemical Properties of the Cyclopentadienyl(benzene)ruthenium(II) Cation. The Synthesis and Reactions of a Synthetically Useful Intermediate: the Cyclopentadienyltris (acetonitrile) ruthenium (II) Cation” Organometallics 1, 485-488. {{DOI|10.1021/om00063a014}}</ref> It is used as a [[homogeneous catalyst]]. It enables C-C bond formation and promotes cycloadditions.<ref>Barry M. Trost, F. Dean Toste, and Anthony B. Pinkerton "Non-Metathesis Ruthenium-Catalyzed C−C Bond Formation" Chem. Rev., 2001, vol. 101, pp 2067–2096. {{DOI|10.1021/cr000666b}}</ref> The ruthenium(II) center is bound in an [[hapticity|η<sup>5</sup>]] manner. |
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==Preparation== |
==Preparation== |
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The title complex is synthesized in two steps from the benzene complex. In the first step, the cyclopentadienyl ligand (Cp<sup>-</sup> is installed using [[cyclopentadienylthallium]]:<ref name=Mann/> |
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The title complex is synthesized by photolysis of [C6H6RuCp]PF6 in acetonitrile solution: |
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[(C6H6)RuCl2]2 +2TiCp + 2NH4PF6 → 2Cp(C6H6)Ru+PF6- +2Ti++2NH4++4Cl- |
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Cp(C6H6)Ru+PF6- + 3MeCN + hν→ CpRu(NCCH3)3 +PF6- + C6H6 <ref>Trost, Barry M; Older, Crhistina, M (2002) “A Convenient Synthetic Route to [CpRu(CH3CN)3]PF6” Organometallics 21. 2544-2546. {{DOI|10.1021/om020143p}} </ref> |
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==Structure== |
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The Ruthenium (II) cation takes on a trigonal bipyramidal structure with a coordination sphere of five. The Cp makes a flat plane above the molecule, while the acetonitrile bonds are linear with the Ruthenium. The electrons in the cyclopentadienyl ring are delocatlized creating an almost equal distance between the carbons and the metal center.<ref>Singhm, Keisham S; Carroll, Patrick J; Kollipara, Mohan R (2005) “Pentamethylcyclopentadienyl ruthenium(II) complexes of para-substituted N-(pyrid-2-ylmethylene)-phenylamine ligands: syntheses, spectral and structural studies” Polyhedron 24, 391-396 </ref> The acetonitrile ligands have a slightly longer than C-Metal bond distance indicating there is some movement among ligands. The structure was reported to be similar to iron complexes and have similar reactivity with a few exceptions. |
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:[(C<sub>6</sub>H<sub>6</sub>)RuCl<sub>2</sub>]<sub>2</sub> + 2 TiCp + 2 NH<sub>4</sub>PF<sub>6</sub> → 2 [Cp(C<sub>6</sub>H<sub>6</sub>)Ru]PF<sub>6</sub> + 2 TiCl + 2 NH<sub>4</sub>Cl |
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The second step entails photolysis of benzene ligand, which is replaced by three equivalents of acetonitrile (MeCN): |
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:[Cp(C<sub>6</sub>H<sub>6</sub>)Ru]PF<sub>6</sub> + 3 MeCN → [CpRu(NCMe)<sub>3</sub>]PF<sub>6</sub> + C<sub>6</sub>H<sub>6</sub> |
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==References== |
==References== |
Revision as of 00:16, 23 November 2013
Identifiers | |
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ECHA InfoCard | 100.152.130 |
CompTox Dashboard (EPA)
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Properties | |
C11H14N3RuPF6 | |
Molar mass | 434.28 |
Appearance | yellow/brown solid |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate is an organoruthenium compound with the formula [(C5H5)Ru(NCCH3)3]PF6, abbreviated [CpRu(NCMe)3]PF6. It is a is a yellow-brown solid that is soluble in polar organic solvents. The compound provides access to effectively RuCp+ for further derivitization.[1] It is used as a homogeneous catalyst. It enables C-C bond formation and promotes cycloadditions.[2] The ruthenium(II) center is bound in an η5 manner.
Preparation
The title complex is synthesized in two steps from the benzene complex. In the first step, the cyclopentadienyl ligand (Cp- is installed using cyclopentadienylthallium:[1]
- [(C6H6)RuCl2]2 + 2 TiCp + 2 NH4PF6 → 2 [Cp(C6H6)Ru]PF6 + 2 TiCl + 2 NH4Cl
The second step entails photolysis of benzene ligand, which is replaced by three equivalents of acetonitrile (MeCN):
- [Cp(C6H6)Ru]PF6 + 3 MeCN → [CpRu(NCMe)3]PF6 + C6H6
References
- ^ a b Gill, Thomas P; Mann, Kent R (1982) “Photochemical Properties of the Cyclopentadienyl(benzene)ruthenium(II) Cation. The Synthesis and Reactions of a Synthetically Useful Intermediate: the Cyclopentadienyltris (acetonitrile) ruthenium (II) Cation” Organometallics 1, 485-488. doi:10.1021/om00063a014
- ^ Barry M. Trost, F. Dean Toste, and Anthony B. Pinkerton "Non-Metathesis Ruthenium-Catalyzed C−C Bond Formation" Chem. Rev., 2001, vol. 101, pp 2067–2096. doi:10.1021/cr000666b