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词条 Pentamethylcyclopentadienyl rhodium dichloride dimer
释义

  1. Structure and preparation

  2. Reactions

  3. Further reading (early literature)

  4. References

{{chembox
| Watchedfields = changed
| verifiedrevid = 428838812
| Name = Pentamethylcyclopentadienyl rhodium dichloride dimer
| ImageFile1 = Cp*2Rh2Cl4new.png
| ImageSize1 = 240
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| ImageFile2 = Cp(star)RhCl2 dimer-2.png
| ImageSize2 = 240px
| ImageName2 = Cp(star)RhCl2 dimer-2
| ImageFile3 = Cp(star)RhCl2 dimer-powder.jpg
| ImageSize3 = 240px
| ImageName3 = Cp(star)RhCl2 dimer-powder
| IUPACName = Di-µ-chloro-bis[chloro(pentamethylcyclopentadienyl)rhodium(III)]
| OtherNames = Dichloro(pentamethylcyclopentadienyl)rhodium(III)
| Section1 = {{Chembox Identifiers
| SMILES =c1(C)=c(C)c(C)=c(C)c1(C)[Rh](Cl)(Cl1)Cl[Rh](Cl)1C1(C)C(C)=C(C)C(C)=C1C
| CASNo = 12354-85-7
| CASNo_Comment = {{cascite|correct|??}}
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| Section2 = {{Chembox Properties
| C=20|H=30|Cl=4|Rh=2
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| Appearance = red solid
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| Solubility = dichloromethane, chloroform
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| Section3 = {{Chembox Structure
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| Section7 = {{Chembox Hazards
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| Section8 = {{Chembox Related
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}}Pentamethylcyclopentadienyl rhodium dichloride is an organometallic compound with the formula [(C5(CH3)5RhCl2)]2, commonly abbreviated [Cp*RhCl2]2 This dark red air-stable diamagnetic solid is a reagent in organometallic chemistry.[1]

Structure and preparation

The compound has idealized C2h symmetry. Each metal centre is pseudo-octahedral.

The compound is prepared by the reaction of rhodium trichloride trihydrate and pentamethylcyclopentadiene in hot methanol, from which the product precipitates:[1]

2 Cp*H   +   2 RhCl3(H2O)3   ->[\\ce{CH3OH} \\text{ / Δ}]   [Cp*RhCl2]2   +   2 HCl   +   6 H2O

It was first prepared by the reaction of hydrated rhodium trichloride with hexamethyl Dewar benzene[2]

{{clear-left}}

Reactions

Reductive carbonylation gives [Cp*Rh(CO)2].[3]

The Rh-μ-Cl bonds are labile and cleave en route to a variety of adducts of the general formula Cp*RhCl2L. Treatment with silver ions in polar solvents causes precipitation of silver(I) chloride, leaving a solution containing dications of the form [Cp*RhL3]2+ (L = H2O, MeCN).

The chemistry is similar to that of the analog pentamethylcyclopentadienyl iridium dichloride dimer.

Further reading (early literature)

  • {{cite journal|last1 = Kang|first1 = Jung W.|last2 = Mosley|first2 = K.|last3 = Maitlis|first3 = Peter M.|authorlink3 = Peter Maitlis|year = 1968|title = Mechanisms of Reactions of Dewar Hexamethylbenzene with Rhodium and Iridium Chlorides|journal = Chem. Commun.|issue = 21|pages = 1304–1305|doi = 10.1039/C19680001304}}
  • {{cite journal|last1 = Kang|first1 = Jung W.|last2 = Maitlis|first2 = Peter M.|authorlink2 = Peter Maitlis|year = 1968|title = Conversion of Dewar Hexamethylbenzene to Pentamethylcyclopentadienylrhodium(III) Chloride|journal = J. Am. Chem. Soc.|volume = 90|issue = 12|pages = 3259–3261|doi = 10.1021/ja01014a063}}
  • {{cite journal|last1 = Criegee|first1 = Rudolf|authorlink1 = Rudolf Criegee|last2 = Grüner|first2 = H.|year = 1968|title = Acid-catalyzed Rearrangements of Hexamethyl-prismane and Hexamethyl-Dewar-benzene|journal = Angew. Chem. Int. Ed.|volume = 7|issue = 6|pages = 467–468|doi = 10.1002/anie.196804672}}
  • {{cite journal|title = Pentamethylcyclopentadienylrhodium and -iridium halides. I. Synthesis and properties|year = 1969|first1 = Jung W.|last1 = Kang|first2 = K.|last2 = Moseley|first3 = Peter M.|last3 = Maitlis|authorlink3 = Peter Maitlis|journal = J. Am. Chem. Soc.|volume = 91|issue = 22|pages = 5970-5977|doi =10.1021/ja01050a008}}
  • {{cite book|title = Synthetic Methods of Organometallic and Inorganic Chemistry – Volume 1: Literature, Laboratory Techniques, and Common Starting Materials|year = 1996|editor1-first = Wolfgang A.|editor1-last = Herrmann|editor2-first = Albrecht|editor2-last = Salzer|publisher = Georg Thieme Verlag|isbn = 9783131791610|chapter = Bis{(μ-chloro)[chloro(η-pentamethylcyclopentadienyl)rhodium]} — {Rh(μ-Cl)Cl[η-C5(CH3)5]}2|first1 = Wolfgang A.|last1 = Herrmann|first2 = Christian|last2 = Zybill|pages = 148-149|url = https://books.google.com.au/books?id=dlGGAwAAQBAJ&pg=PA148}}
  • {{cite book|url = https://books.google.com.au/books?id=VmE2BtDmHjYC&pg=PA116|title = Organotransition Metal Chemistry: A Mechanistic Approach|first = Richard F.|last = Heck|authorlink = Richard F. Heck|publisher = Academic Press|year = 1974|isbn = 9780323154703|chapter = Reactions of Dienes Trienes and Tetraenes with Transition Metal Compounds|pages = 116-117}}

References

1. ^1 {{cite journal|title = (η5-Pentamethylcyclopentadienyl)Rhodium and -Iridium Compounds|year = 1992|last1 = White|first1 = C.|last2 = Yates|first2 = A.|last3 = Maitlis|first3 = Peter M.|authorlink3 = Peter Maitlis| journal = Inorg. Synth.|volume = 29|pages = 228–234|doi = 10.1002/9780470132609.ch53}}
2. ^{{cite journal|last1 = Paquette|first1 = Leo A.|authorlink1 = Leo Paquette|last2 = Krow|first2 = Grant R.|year = 1968|title = Electrophilic Additions to Hexamethyldewarbenzene|journal = Tetrahedron Lett.|volume = 9|issue = 17|pages = 2139–2142|doi = 10.1016/S0040-4039(00)89761-0}}
3. ^{{cite book|title = Synthetic Methods of Organometallic and Inorganic Chemistry – Volume 1: Literature, Laboratory Techniques, and Common Starting Materials|year = 1996|editor1-first = Wolfgang A.|editor1-last = Herrmann|editor2-first = Albrecht|editor2-last = Salzer|publisher = Georg Thieme Verlag|isbn = 9783131791610|chapter = Dicarbonyl(η-pentamethylcyclopentadienyl)rhodium — Rh[η-C5(CH3)5](CO)2|first1 = Wolfgang A.|last1 = Herrmann|first2 = Christian|last2 = Zybill|pages = 147-148|url = https://books.google.com.au/books?id=dlGGAwAAQBAJ&pg=PA147}}
{{Rhodium compounds}}

4 : Organorhodium compounds|Dimers (chemistry)|Pentamethylcyclopentadienyl complexes|Chloro complexes
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