|Title:||Mechanistic studies of olefin metathesis by ruthenium carbene complexes using electrospray ionization tandem mass spectrometry|
|Authors :||Adlhart, Christian|
|Published in :||Journal of the American Chemical Society|
|Publisher / Ed. Institution :||American Chemical Society|
|Language :||Englisch / English|
|Subject (DDC) :||540: Chemie|
|Abstract:||The olefin metathesis reaction of the Grubbs ruthenium carbene complexes has been investigated in the gas phase by electrospray ionization tandem mass spectrometry. Relative rates of reaction for substituted ruthenium benzylidenes and alkylidenes after removal of one phosphine ligand were interpreted with the aid of linear free energy anal. and kinetic isotope effects. The exptl. observations are consistent with a reaction profile in which the metallacyclobutane structure is a transition state rather than an intermediate, although alternative explanations cannot be wholly ruled out. Electron withdrawal on the carbene moiety is found to accelerate the metathesis reaction when only the metathesis step itself is examd. Quantum chem. calcns. at a variety of levels were performed to check for the consistency of the interpretation.|
|Departement:||Life Sciences und Facility Management|
|Organisational Unit:||Institut für Chemie und Biotechnologie (ICBT)|
|Publication type:||Beitrag in wissenschaftlicher Zeitschrift / Article in scientific Journal|
|Type of review:||Peer review (Publikation)|
|License (according to publishing contract) :||Lizenz gemäss Verlagsvertrag / Licence according to publishing contract|
|Appears in Collections:||Publikationen Life Sciences und Facility Management|
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