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Modes of Reactivity of Cyclic Diynes: Probing the syn / anti Selectivity of Tetrathiacycloalkadiynes and Mono(alkyne)cobalt Complexes
Author(s) -
Benisch Christoph,
Werz Daniel B.,
Gleiter Rolf,
Rominger Frank,
Oeser Thomas
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.200390141
Subject(s) - cyclobutadiene , chemistry , metallacycle , reactivity (psychology) , alkyne , cyclopentadienyl complex , acetylene , cobalt , stereochemistry , selectivity , crystallography , medicinal chemistry , molecule , x ray crystallography , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , diffraction , optics
Cyclic tetrathiaalkadiynes in which two 1,4‐dithiaalkyne units are connected with alkane bridges of length n and m [ A( m.n ) ] were treated with [η 2 ‐bis( tert ‐butylsulfonyl)acetylene]carbonyl(η 5 ‐cyclopentadienyl)cobalt( I ) ( 8a ) and several substituted analogues ( 8b − 8e ) in order to probe the reactivity of electron‐rich cyclic diynes. Both mono‐ [ B( m.n ) ] and bis(cyclobutadiene) [ C( m.n ) ] complexes were isolated as products of these reactions and the anti / syn ratio of C( m.n ) was determined. For m , n < 4 the syn isomers dominate and this is attributed to the configuration of the intermediate metallacycle which is correlated with the conformations of the rings in the mono(cyclobutadiene) products B( m.n ) . This analysis was corroborated by X‐ray structural investigations of the products. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)