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Elementary Reactions at Metal–Sulfur Centers: Base‐Induced Substitution of PPh 3 in [Ru(PPh 3 ) 2 (bmae)]
Author(s) -
Sellmann Dieter,
Käppler Olaf
Publication year - 1988
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198806891
Subject(s) - ruthenium , chemistry , sulfur , reactivity (psychology) , substitution reaction , substitution (logic) , sulfite , metal , base (topology) , medicinal chemistry , stereochemistry , inorganic chemistry , catalysis , organic chemistry , medicine , mathematical analysis , alternative medicine , mathematics , pathology , computer science , programming language
Model reactions to gain an understanding of the mode of interaction of numerous oxidoreductases (from sulfite oxidase to nitrogenases) have been carried out on the ruthenium complexes 1 and 2 . In the case of 1 , PPh 3 is rapidly replaced by CO (1 bar) already at room temperature; in the case of the title compound 2 the same reaction can only be initiated by addition of bases, which first deprotonate the σ‐donor amino functions. These findings show that the ligands can drastically influence the reactivity of the metal center in substitution reactions and are pH dependent (bmae 2⊖ = 2,2‐ethylenediiminobis(thiophenolate)).