| Publikationstyp: | Beitrag in wissenschaftlicher Zeitschrift |
| Art der Begutachtung: | Peer review (Publikation) |
| Titel: | Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis |
| Autor/-in: | Volland, Martin A. O. Adlhart, Christian Kiener, Christoph A. Hofmann, Peter |
| DOI: | 10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C |
| Erschienen in: | Chemistry - A European Journal |
| Band(Heft): | 7 |
| Heft: | 21 |
| Seite(n): | 4621 |
| Seiten bis: | 4632 |
| Erscheinungsdatum: | 5-Nov-2001 |
| Verlag / Hrsg. Institution: | Wiley |
| Verlag / Hrsg. Institution: | Hoboken |
| ISSN: | 0947-6539 1521-3765 |
| Sprache: | Englisch |
| Fachgebiet (DDC): | 540: Chemie |
| Zusammenfassung: | A screening methodol. combines in situ synthesis of complexes with an assay by electrospray ionization tandem mass spectrometry (ESI-MS) for evaluation of highly active, cationic ruthenium-carbene catalysts in ring-opening metathesis polymn. (ROMP). The parameter space, which is defined by systematic variation of four structural features of the catalyst [{R2P(CH2)nPR2-κ2P}XRu=CHR']+ (the halogen ligand, the diphosphane bite-angle, the steric bulk of the phosphane, and the carbene ligand) and the variation of the metathesis substrate, is mapped out. The 180 reactions (repeated 10 times each) were carried out in two weeks to map out the parameter space. Chloride as the anionic ligand X, a small chelating angle (n = 1), and reduced steric demand of the substituents R (Cy vs. tBu) lead to the most reactive complex in acyclic olefin metathesis, whereas variation of the carbene moiety CHR' has only a modest influence. The overall reaction rate in the gas phase depends on the π-complex preequil. and metallacyclobutane formation, the rate-detg. step. In ROMP reactions backbiting has a profound influence on the overall rate. The reactivity trends detd. in the gas phase parallel soln.-phase reactivity. The overall rate in soln. was also detd. by a favorable dimer/monomer preequil. providing the active catalyst by facile dissocn. of dicationic, dinuclear catalyst precursors. |
| URI: | https://digitalcollection.zhaw.ch/handle/11475/2093 |
| Volltext Version: | Publizierte Version |
| Lizenz (gemäss Verlagsvertrag): | Lizenz gemäss Verlagsvertrag |
| Departement: | Life Sciences und Facility Management |
| Organisationseinheit: | Institut für Chemie und Biotechnologie (ICBT) |
| Enthalten in den Sammlungen: | Publikationen Life Sciences und Facility Management |
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Volland, M. A. O., Adlhart, C., Kiener, C. A., & Hofmann, P. (2001). Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis. Chemistry - A European Journal, 7(21), 4621–4632. https://doi.org/10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C
Volland, M.A.O. et al. (2001) ‘Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis’, Chemistry - A European Journal, 7(21), pp. 4621–4632. Available at: https://doi.org/10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C.
M. A. O. Volland, C. Adlhart, C. A. Kiener, and P. Hofmann, “Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis,” Chemistry - A European Journal, vol. 7, no. 21, pp. 4621–4632, Nov. 2001, doi: 10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C.
VOLLAND, Martin A. O., Christian ADLHART, Christoph A. KIENER und Peter HOFMANN, 2001. Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis. Chemistry - A European Journal. 5 November 2001. Bd. 7, Nr. 21, S. 4621–4632. DOI 10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C
Volland, Martin A. O., Christian Adlhart, Christoph A. Kiener, and Peter Hofmann. 2001. “Catalyst Screening by Electrospray Ionization Tandem Mass Spectrometry : Hofmann Carbenes for Olefin Metathesis.” Chemistry - A European Journal 7 (21): 4621–32. https://doi.org/10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C.
Volland, Martin A. O., et al. “Catalyst Screening by Electrospray Ionization Tandem Mass Spectrometry : Hofmann Carbenes for Olefin Metathesis.” Chemistry - A European Journal, vol. 7, no. 21, Nov. 2001, pp. 4621–32, https://doi.org/10.1002/1521-3765(20011105)7:21<4621::AID-CHEM4621>3.0.CO;2-C.
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