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Ruthenium‐Catalyzed Transvinylation – New Insights
Author(s) -
Ziriakus Jennifer,
Zimmermann. Teresa K.,
Pöthig Alexander,
Drees Markus,
Haslinger Stefan,
Jantke Dominik,
Kühn Fritz E.
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300447
Subject(s) - ruthenium , chemistry , catalysis , carboxylate , combinatorial chemistry , photochemistry , stereochemistry , organic chemistry
The use of ruthenium complexes in transvinylation catalysis has been well established since the 1980s. However, the reaction mechanism and the active catalyst species, which is presumed to contain ruthenium carbonyl carboxylate entities, have so far remained elusive. In this work the synthesis and characterization of three novel ruthenium complexes comprising ruthenium carbonyl carboxylate structural motifs including two single crystal structures as well as the crystal structures of two known ruthenium complexes are reported. These new complexes and four known ruthenium complexes with appropriate structural motifs were applied in transvinylation catalysis. Mechanistic studies including identification and characterization of the active species, isotope labeling experiments and examination of the regio‐ and stereoselectivity of the transvinylation reaction are presented, resulting in the proposal of a probable reaction mechanism, which is supported by DFT calculations on the B3LYP/6‐31G* level of theory.