Zirconocene Functional Group Chemistry: Photochemical [4+4] Cycloaddition of Isoprenyl Sidechains to the Bent Metallocene Framework | Zendy

Greger Ingo | Zendy; Kehr Gerald | Zendy; Erker Gerhard | Zendy

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Zirconocene Functional Group Chemistry: Photochemical [4+4] Cycloaddition of Isoprenyl Sidechains to the Bent Metallocene Framework

Author(s) -

Greger Ingo,

Kehr Gerald,

Erker Gerhard

Publication year - 2010

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.201000432

Subject(s) - chemistry , fulvene , deprotonation , metallocene , cycloaddition , transmetalation , intramolecular force , medicinal chemistry , metathesis , photodissociation , stereochemistry , photochemistry , organic chemistry , catalysis , polymerization , ion , polymer

The 4‐isoprenyl‐ and 1‐isoprenylcyclopentadienides 6a and 6b were prepared by means of a fulvene route involving a subsequent deprotonation reaction using potassium hexamethyldisilylamide. Transmetallation to zirconium or hafnium gave the respective bis(4‐isoprenyl‐Cp)MCl 2 and bis(1‐isoprenyl‐Cp)MCl 2 complexes 7a , b and 8a , b , respectively. Upon photolysis, the (4‐isoprenyl‐Cp) 2 ZrCl 2 and ‐HfCl 2 complexes 7a , 8a underwent rapid intramolecular [4+4] cycloaddition reactions to yield the cyclooctadienylene‐bridged ansa ‐metallocenes 9a , 10a in high yields.

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