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Halogen Atoms as Reactive Centers for the Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
Author(s) -
Bodes Gregor,
Heinemann Frank W.,
Jobi Günter,
Klodwig Jens,
Neumann Stefan,
Zenneck Ulrich
Publication year - 2003
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.200390038
Subject(s) - chemistry , ruthenium , enantiopure drug , electrophile , medicinal chemistry , halogen , cyclooctadiene , ligand (biochemistry) , aryl , metalation , diastereomer , cationic polymerization , naphthalene , stereochemistry , organic chemistry , enantioselective synthesis , catalysis , biochemistry , alkyl , receptor
Substitution of the naphthalene ligand of [(COD)(η 6 ‐naphthalene)Ru] ( 2 ) (COD = 1,5‐cyclooctadiene) by suitable haloarenes (halogen = F, Cl, Br, I) affords several new mono‐ and dihaloarene(cyclooctadiene)ruthenium complexes. Depending on the number and position of the halogen and organyl substituents, the haloarenes form achiral or planar‐chiral π‐ligands; [(η 6 ‐bromoarene)(COD)Ru] complexes are prone to rapid bromine/lithium exchange with n BuLi at low temperatures, while the chloro and fluoro derivatives undergo ortho ‐metalation under the same conditions. The lithiated species react readily with chiral or achiral electrophiles such as chlorodiorganophosphanes, carbonyl chlorides, aldehydes, lactones, ketones, and epoxides to yield substituted [(η 6 ‐arene)(COD)Ru] complexes with donor functions in their side chains, inaccessible by other routes. Enantiopure complexes are obtained when achiral lithioarene complexes are combined with chiral electrophiles, but pairs of diastereomers are formed if the lithioarene ligand is a planar‐chiral species. Dinuclear ruthenium complexes [1,1‐bis{(COD)(η 6 ‐phenyl)Ru}‐1,4‐butanediol] ( 28 ) and [1,1‐bis{(COD)(η 6 ‐4‐fluorophenyl)Ru}‐1,4‐butanediol] ( 30 ) with two (η 6 ‐aryl)(COD)Ru units linked by a common 1,4‐butanediol side chain are formed through the reactions between the appropriate lithioarene complexes and γ‐butyrolactone. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2003)