| Revision as of 23:17, 12 May 2011 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'UNII_Ref', 'ChemSpiderID_Ref', 'StdInChI_Ref', 'StdInChIKey_Ref', 'ChEMBL_Ref', 'KEGG_Ref') per Chem/Drugbox validation (← Previous edit |
Latest revision as of 01:46, 22 June 2024 edit undoCitation bot (talk | contribs)Bots5,391,003 edits Altered title. Added chapter. Removed parameters. | Use this bot. Report bugs. | #UCB_CommandLine |
| (41 intermediate revisions by 24 users not shown) |
| Line 1: |
Line 1: |
|
{{chembox |
|
{{chembox |
|
|
| Watchedfields = changed |
|
| verifiedrevid = 411927247 |
|
| verifiedrevid = 428838812 |
|
| Name = Pentamethylcyclopentadienyl iridium dichloride dimer |
|
| Name = Pentamethylcyclopentadienyl iridium dichloride dimer |
|
| ImageFile = Cp*IrCl2dimer.png |
|
| ImageFile = Cp*2Ir2Cl4 2023.svg |
|
| ImageSize = 240 |
|
| ImageSize = 240 |
|
| ImageName = |
|
| ImageName = |
|
| IUPACName = Di-µ-chloro-bis |
|
| IUPACName = Di-''μ''-chloro-bis |
|
| OtherNames = Dichloro(pentamethylcyclopentadienyl)iridium(III) |
|
| OtherNames = Dichloro(pentamethylcyclopentadienyl)iridium(III) |
|
| Section1 = {{Chembox Identifiers |
|
| Section1 = {{Chembox Identifiers |
|
|
| SMILES = c1(C)=c(C)c(C)=c(C)c1(C)(Cl)(Cl1)Cl(Cl)1C1(C)C(C)=C(C)C(C)=C1C |
|
| SMILES = |
|
|
|
| CASNo_Ref = {{cascite|correct|??}} |
|
| CASNo = 12354-84-6 |
|
| CASNo = 12354-84-6 |
|
| RTECS = |
|
| RTECS = |
|
|
| PubChem = 131674877 |
|
|
| UNII = 6OY4UUC534 |
|
|
| InChI=1S/2C10H16.4ClH.2Ir/c2*1-6-7(2)9(4)10(5)8(6)3;;;;;;/h2*6H,1-5H3;4*1H;;/p-4 |
|
|
| InChIKey = PGQVOTGCKISIMD-UHFFFAOYSA-J |
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
| Section2 = {{Chembox Properties |
| Line 17: |
Line 23: |
|
| Appearance = orange solid |
|
| Appearance = orange solid |
|
| Density = |
|
| Density = |
|
| Solubility = |
|
| Solubility = Dichloromethane, Chloroform |
|
| MeltingPt = >230 °C |
|
| MeltingPt = >230 °C |
|
| BoilingPt = |
|
| BoilingPt = |
| Line 34: |
Line 40: |
|
| MainHazards = |
|
| MainHazards = |
|
| FlashPt = |
|
| FlashPt = |
|
| RPhrases = |
|
| HPhrases = |
|
| SPhrases = |
|
| PPhrases = |
|
|
| GHS_ref = |
|
}} |
|
}} |
|
| Section8 = {{Chembox Related |
|
| Section8 = {{Chembox Related |
|
| OtherAnions = |
|
| OtherAnions = |
| Line 44: |
Line 51: |
|
}} |
|
}} |
|
|
|
|
|
'''Pentamethylcyclopentadienyl iridium dichloride''' is an ] compound with the formula <sub>2</sub>, commonly abbreviated <sub>2</sub> This bright orange air stable ] solid is a reagent in organometallic chemistry.<ref name=Mailtlis/> |
|
'''Pentamethylcyclopentadienyl iridium dichloride dimer''' is an ] compound with the formula <sub>2</sub>, commonly abbreviated <sub>2</sub> This bright orange air-stable ] solid is a reagent in organometallic chemistry.<ref name=Mailtlis/> |
|
|
|
|
|
|
==Structure== |
| ⚫ |
==Preparation, structure, reactions== |
|
|
The compound has C<sub>2h</sub> ]. Each metal is pseudo-octahedral. It was first prepared by the reaction of hydrated ] with hexamethyl].<ref>{{cite journal | doi =10.1021/ja01050a008 | title =Pentamethylcyclopentadienylrhodium and -iridium halides. I. Synthesis and properties | year =1969 | author =Jung W. Kang; K. Moseley; ] | journal =Journal of the American Chemical Society | volume =91 | pages =5970}} |
|
The compound has C<sub>2h</sub> ]. Each metal is pseudo-octahedral. The terminal and bridging Ir-Cl bonds have the lengths 2.39 and 2.45 Å, respectively. |
|
|
|
|
</ref> More conveniently, iridium trihydrate and ] consistently gives the product in both high yield and purity according to this idealized equation:<ref name=Mailtlis>{{cite journal | doi = 10.1002/9780470132609.ch53 | title = (η<sup>5</sup>-Pentamethylcyclopentadienyl)Rhodium and -Iridium Compounds | year = 1992 | author1 = White, C. | author2 = Yates, A. | author3 = Maitlis, P. M. |authorlink3 = Peter Maitlis| journal =Inorganic Syntheses| volume = 29 | pages = 228–234| DUPLICATE DATA: doi = 10.1002/9780470132609.ch53}}</ref> |
|
|
⚫ |
==Preparation, reactions== |
|
|
Pentamethylcyclopentadienyl iridium dichloride dimer was first prepared by the reaction of hydrated ] with ].<ref>{{cite journal | doi =10.1021/ja01050a008 | title = Pentamethylcyclopentadienylrhodium and -iridium halides. I. Synthesis and properties | year = 1969 | first1 = Jung W.| last1 = Kang | first2 = K. | last2 = Moseley | author3-link = Peter M. Maitlis | first3 = Peter M. | last3 = Maitlis | journal =] | volume = 91 | issue = 22 | pages = 5970–5977}}</ref> More conveniently, the compound is prepared by the reaction of hydrated iridium trichloride and ] in hot methanol, from which the product precipitates<ref name=Mailtlis>{{cite book | doi = 10.1002/9780470132609.ch53 | title = Inorganic Syntheses | year = 1992 | last1 = White | first1 = C. | last2 = Yates | first2 = A. | last3 = Maitlis | first3 = P. M. | chapter = (η <sup>5</sup> -Pentamethylcyclopentadienyl)Rhodium and -Iridium Compounds | authorlink3 = Peter Maitlis | journal =] | volume = 29 | pages = 228–234| isbn = 9780471544708 }}</ref> |
|
:2 Cp*H + 2 IrCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub> → <sub>2</sub> + 2 HCl + 6 H<sub>2</sub>O |
|
:2 Cp*H + 2 IrCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub> → <sub>2</sub> + 2 HCl + 6 H<sub>2</sub>O |
|
|
|
|
|
The two Ir-]-Cl bonds are labile and can be cleaved to give a variety of adducts of the general formula Cp*IrCl<sub>2</sub>L. Such adducts undergo further substitution to afford cations <sup>+</sup> and <sup>2+</sup>. The chloride ligands can also be replaced by other anions such as ], ], and ]. |
|
The Ir-'']''-Cl bonds are labile and can be cleaved to give a variety of adducts of the general formula Cp*IrCl<sub>2</sub>L. Such adducts undergo further substitution to afford cations {{nowrap|<sup>+</sup>}} and <sup>2+</sup>. The chloride ligands can also be replaced by other anions such as ]s, ], and ]. |
|
|
|
|
|
Reduction of <sub>2</sub> in the presence of CO affords , which can be decarbonylated to give the unsaturated derivative <sub>2</sub>.<ref>{{cite journal | doi = 10.1021/ic00335a051 | title = Synthesis and structure of dicarbonylbis(η-pentamethylcyclopentadienyl)diiridium | year = 1990 | first1 = R. G. | last1 = Ball | first2 = W. A. G.| last2 = Graham | first3 = D. M. | last3 = Heinekey | first4 = J. K. | last4 = Hoyano | first5 = A. D. | last5 = McMaster | first6 = B. M. | last6 = Mattson | first7 = S. T. | last7 = Michel | journal = ] | volume = 29 | issue = 10 | pages = 2023–2025}}</ref> Treatment of <sub>2</sub> with ] under an atmosphere of H<sub>2</sub> gives the iridium(V) derivative Cp*IrH<sub>4</sub>. |
|
|
|
|
|
Reduction of <sub>2</sub> under an atmosphere of CO affords the dicarbonyl Cp*Ir(CO)<sub>2</sub>], which can be decarbonylated to give the unsaturated derivative <sub>2</sub>.<ref>{{cite journal | doi =10.1021/ic00335a051 | title =Synthesis and structure of dicarbonylbis(.eta.-pentamethylcyclopentadienyl)diiridium | year =1990 | author =R. G. Ball; W. A. G. Graham; D. M. Heinekey; J. K. Hoyano; A. D. McMaster; B. M. Mattson; S. T. Michel | journal =Inorganic Chemistry | volume =29 | pages =2023}}</ref> Treatment of <sub>2</sub> with ] under an atmosphere of H<sub>2</sub> gives the iridium(V) derivative Cp*IrH<sub>4</sub>. |
|
<sub>2</sub> is a precursor to catalysts for the asymmetric ] of ketones.<ref>{{cite journal | doi = 10.1021/ar700134q | year = 2007 | last1 = Ikariya | first1 = T. | last2 = Blacker | first2 = A. J. | title = Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts | volume = 40 | issue = 12 | pages = 1300–1308 | pmid = 17960897 | journal = ]}}</ref> |
|
|
|
|
|
|
==Related compounds== |
|
<sub>2</sub> is a precursor to catalysts for the asymmetric ] of ketones.<ref>{{cite journal | doi = 10.1021/ar700134q | year = 2007 | month = Dec | author = Ikariya, T.; Blacker, A. J. | title = Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts | volume = 40 | issue = 12 | pages = 1300–8 | issn = 0001-4842 | pmid = 17960897 | journal = Accounts of Chemical Research}}</ref> |
|
|
|
*The 16e monomer (])IrCl<sub>2</sub><ref>{{cite journal|doi=10.1246/cl.160937|title=Half-sandwich Cyclopentadienyl Iridium Dichloride Monomer Cp<sup>‡</sup>IrCl<sub>2</sub> (Cp<sup>‡</sup> = 1,2,4-tri-''tert''-butylcyclopentadienyl)|year=2017|last1=Shimogawa|first1=Ryuichi|last2=Takao|first2=Toshiro|last3=Suzuki|first3=Hiroharu|journal=Chemistry Letters|volume=46|issue=2|pages=197–199}}</ref> |
|
|
* ] |
|
|
|
|
|
==References== |
|
==References== |
|
<references/> |
|
<references/> |
|
|
|
|
|
|
{{Authority control}} |
|
] |
|
] |
|
] |
|
] |
|
|
] |
|
|
] |
|
|
] |