Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis

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

Publication type:	Article in scientific journal
Type of review:	Peer review (publication)
Title:	Catalyst screening by electrospray ionization tandem mass spectrometry : Hofmann carbenes for olefin metathesis
Authors:	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
Published in:	Chemistry - A European Journal
Volume(Issue):	7
Issue:	21
Page(s):	4621
Pages to:	4632
Issue Date:	5-Nov-2001
Publisher / Ed. Institution:	Wiley
Publisher / Ed. Institution:	Hoboken
ISSN:	0947-6539 1521-3765
Language:	English
Subject (DDC):	540: Chemistry
Abstract:	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
Fulltext version:	Published version
License (according to publishing contract):	Licence according to publishing contract
Departement:	Life Sciences and Facility Management
Organisational Unit:	Institute of Chemistry and Biotechnology (ICBT)
Appears in collections:	Publikationen Life Sciences und Facility Management

Files in This Item:

There are no files associated with this item.

Show full item record

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.