Sumans

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Structural formula
Structural formula of Sumanen
Crystal system

rhombohedral

Space group

R 3 c (No. 161)Template: room group / 161

Lattice parameters

a = 16.6402 Å, c = 7.7024 Å

General
Surname Sumans
other names
  • 4,7-dihydro-1 H -tricyclopenta [ def , jkl , pqr ] triphenylene ( IUPAC )
Molecular formula C 21 H 12
External identifiers / databases
CAS number 151253-59-7
PubChem 11173107
ChemSpider 9348199
Wikidata Q2303663
properties
Molar mass 264.32 g mol −1
Melting point

115 ° C

safety instructions
GHS hazard labeling
no classification available
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Sumanen (from Hindi सुमन 'suman' ) is an organic compound from the group of polycyclic aromatic hydrocarbons . The compound is structurally related to corannulene and Buckminster fullerenes .

presentation

The first attempt at synthesis was made in 1993 starting from tris (bromomethyl) triphenylene , but was unsuccessful. It was only ten years later that the connection was successfully represented in solution. For this purpose, norbornadiene was reacted with butyllithium , KO t -Bu and 1,2-dibromoethane with strong cooling in THF , and copper (I) iodide was added at room temperature . Created here both syn - and anti - Benzotris (norbornadiene) , the what syn -product means of the Grubbs I - catalyst was reacted in the cold to form an intermediate product from which by reaction with DDQ under heating in toluene was sumanene.

Reaction scheme for the representation of sumans

properties

Cup-shaped structure

The structure consists of a benzene ring surrounded by alternating three benzene and three cyclopentadiene rings . The compound does not have a planar structure, instead a shell-shaped C 3 -symmetrical framework is present. Its shell depth is 1.1 Å with a curvature of 8.8 °. The inversion barrier of the shell structure is 19.6  kcal · mol −1 , which means that the barrier is significantly higher than that of corannulene. Sumanen crystallizes in the rhombohedral space group R 3 c (space group no. 161) with the lattice constants a = 16.6402 Å, c = 7.7024 Å. Template: room group / 161

The shells are in a layered structure, which is why the suitability for anisotropic charge carrier transport is being investigated.

Some heterosumanenes with, for example, nitrogen , sulfur , silicon but also germanium or selenium are known as heteroatoms.

use

The connection is largely of academic interest.

Analogously to fluorene , the compound has a benzylic position at which the compound can undergo alkylations and aldol condensations . Anions are stabilized in the corresponding positions, the representation of the trianion is possible by gradually adding t -BuLi . Accordingly, derivatizations of Sumanen with electrophiles are possible.

Sumanen is occasionally used as a ligand . The selective synthesis of concave bound Sumanen was achieved using the complex [CpFe (Sumanen)] [PF 6 ], which according to the authors is the first report on a concave binding, bowl-shaped π complex. Other complexes shown are the ruthenocene derivative [CpRu (η 6 ‐Sumanen)] [PF 6 ] and the zirconocene derivative [Cp (sumanenyl) ZrCl 2 ] (also with Cp * ligand), in which there is an inversion between concave and convex coordination takes place.

Individual evidence

  1. ↑ a b H. Sakurai, T. Daiko, H. Sakane, T. Amaya, T. Hirao: CCDC 266603: Experimental Crystal Structure Determination . In: The Cambridge Crystallographic Data Center . March 2005, doi : 10.5517 / cc8yf3q .
  2. ↑ Sumanene. In: tcichemicals.com. TCI Japan, accessed April 8, 2019 .
  3. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
  4. ↑ a b c Jay S. Siegel, Yao-Ting Wu (Ed.): Polyarenes . Springer, 2014, ISBN 978-3-662-43379-9 , pp. 97-104 ( limited preview in Google Book Search [accessed April 8, 2019]).
  5. ↑ Goverdhan Mehta, Shailesh R. Shahk, K. Ravikumarc: Towards the design of tricyclopenta [def, jkl, pqr] triphenylene ('sumanene') . A 'bowl-shaped' hydrocarbon featuring a structural motif present in C 60 (buckminster fullerene). In: Journal of the Chemical Society , Chemical Communications . tape 0 , no. 12 , 1993, doi : 10.1039 / C39930001006 .
  6. ↑ Hidehiro Sakurai, Taro Daiko, Toshikazu Hirao: A Synthesis of Sumanene, a Fullerene Fragment . In: Science . tape 301 , no. 5641 , September 2003, p. 1878 , doi : 10.1126 / science.1088290 .
  7. ↑ Shuhei Higashibayashi, Hidehiro Sakurai: Synthesis of Sumanene and Related Buckybowls . In: Chemistry Letters . tape 40 , no. 2 , 2011, p. 122–128 , doi : 10.1246 / cl.2011.122 .
  8. ↑ a b Toru Amaya, Toshikazu Hirao: Chemistry of Sumanene . In: The Chemical Record . tape 15 , no. 1 , 2015, p. 310-321 , doi : 10.1002 / tcr.201402078 .
  9. ^ Qian Miao: Polycyclic Arenes and Heteroarenes . Synthesis, Properties, and Applications. John Wiley & Sons , 2015, ISBN 978-3-527-33847-4 , chap. 3 , p. 68 ( limited preview in Google Book Search [accessed April 8, 2019]).
  10. ↑ Toshikazu Hirao (Ed.): Functionalized Redox Systems . Synthetic Reactions and Design of π- and Bio-Conjugates. Springer, 2015, ISBN 978-4-431-55306-9 , 3.9, pp. 102-104 ( limited preview in Google Book Search [accessed April 8, 2019]).