On the mechanism of imine elimination from Fischer tungsten carbene complexes
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- Philipp Veit
- Christoph Foerster
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000378762900001&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.3762/bjoc.12.125
- Externe Identifier
- Clarivate Analytics Document Solution ID: DP8QO
- PubMed Identifier: 27559381
- ISSN
- 1860-5397
- Zeitschrift
- BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
- Schlüsselwörter
- carbene complexes
- ferrocene
- imine
- mechanism
- tungsten
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Titel
- On the mechanism of imine elimination from Fischer tungsten carbene complexes
- Sub types
- Article
- Ausgabe der Zeitschrift
- 12
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Abstract
- <jats:p>(Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)<jats:sub>5</jats:sub>W=C(NHFc)Fc (<jats:bold>W(CO)</jats:bold><jats:bold><jats:sub>5</jats:sub></jats:bold><jats:bold>(</jats:bold><jats:bold><jats:italic>E</jats:italic></jats:bold><jats:bold>-2)</jats:bold>) is synthesized by nucleophilic substitution of the ethoxy group of (CO)<jats:sub>5</jats:sub>W=C(OEt)Fc (<jats:bold>M(CO)</jats:bold><jats:bold><jats:sub>5</jats:sub></jats:bold><jats:bold>(1</jats:bold><jats:bold><jats:sup>Et</jats:sup></jats:bold><jats:bold>)</jats:bold>) by ferrocenyl amide Fc-NH<jats:sup>–</jats:sup> (Fc = ferrocenyl). <jats:bold>W(CO)</jats:bold><jats:bold><jats:sub>5</jats:sub></jats:bold><jats:bold>(</jats:bold><jats:bold><jats:italic>E</jats:italic></jats:bold><jats:bold>-2)</jats:bold> thermally and photochemically eliminates bulky <jats:italic>E</jats:italic>-1,2-diferrocenylimine (<jats:bold><jats:italic>E</jats:italic></jats:bold><jats:bold>-3</jats:bold>) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine <jats:bold><jats:italic>E</jats:italic></jats:bold><jats:bold>-3</jats:bold> are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. <jats:bold>W(CO)</jats:bold><jats:bold><jats:sub>5</jats:sub></jats:bold><jats:bold>(</jats:bold><jats:bold><jats:italic>E</jats:italic></jats:bold><jats:bold>-2)</jats:bold> decays thermally in a first-order rate-law with a Gibbs free energy of activation of Δ<jats:italic>G</jats:italic><jats:sup>‡</jats:sup><jats:sub>298K</jats:sub> = 112 kJ mol<jats:sup>−1</jats:sup>. Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent) densitiy functional theory [(TD)-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II) intermediates <jats:bold><jats:italic>cis</jats:italic></jats:bold><jats:bold>(N,H)-W(CO)</jats:bold><jats:bold><jats:sub>4</jats:sub></jats:bold><jats:bold>(H)(</jats:bold><jats:bold><jats:italic>Z</jats:italic></jats:bold><jats:bold>-15)</jats:bold> and <jats:bold><jats:italic>cis</jats:italic></jats:bold><jats:bold>(C,H)-W(CO)</jats:bold><jats:bold><jats:sub>4</jats:sub></jats:bold><jats:bold>(H)(</jats:bold><jats:bold><jats:italic>Z</jats:italic></jats:bold><jats:bold>-15)</jats:bold>.</jats:p>
- Date of acceptance
- 2016
- Autoren
- Philipp Veit
- Christoph Förster
- Katja Heinze
- DOI
- 10.3762/bjoc.12.125
- eISSN
- 1860-5397
- Zeitschrift
- Beilstein Journal of Organic Chemistry
- Sprache
- en
- Online publication date
- 2016
- Paginierung
- 1322 - 1333
- Status
- Published online
- Herausgeber
- Beilstein Institut
- Herausgeber URL
- http://dx.doi.org/10.3762/bjoc.12.125
- Datum der Datenerfassung
- 2021
- Titel
- On the mechanism of imine elimination from Fischer tungsten carbene complexes
- Ausgabe der Zeitschrift
- 12
Data source: Crossref
- Abstract
- (Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO) 5 ( E -2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO) 5 (1 (Et) )) by ferrocenyl amide Fc-NH(-) (Fc = ferrocenyl). W(CO) 5 ( E -2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine ( E -3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E -3 are performed by NMR, IR and UV-vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO) 5 ( E -2) decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG (‡) 298K = 112 kJ mol(-1). Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent) densitiy functional theory [(TD)-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II) intermediates cis (N,H)-W(CO) 4 (H)( Z -15) and cis (C,H)-W(CO) 4 (H)( Z -15).
- Addresses
- Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg-University, Duesbergweg 10-14, 55128 Mainz, Germany.
- Autoren
- Philipp Veit
- Christoph Förster
- Katja Heinze
- DOI
- 10.3762/bjoc.12.125
- eISSN
- 1860-5397
- Externe Identifier
- PubMed Identifier: 27559381
- PubMed Central ID: PMC4979739
- Open access
- true
- ISSN
- 1860-5397
- Zeitschrift
- Beilstein journal of organic chemistry
- Sprache
- eng
- Medium
- Electronic-eCollection
- Online publication date
- 2016
- Open access status
- Open Access
- Paginierung
- 1322 - 1333
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Publisher licence
- CC BY
- Datum der Datenerfassung
- 2016
- Titel
- On the mechanism of imine elimination from Fischer tungsten carbene complexes.
- Sub types
- research-article
- Journal Article
- Ausgabe der Zeitschrift
- 12
Files
https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-12-125.pdf https://europepmc.org/articles/PMC4979739?pdf=render
Data source: Europe PubMed Central
- Abstract
- (Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO) 5 ( E -2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO) 5 (1 (Et) )) by ferrocenyl amide Fc-NH(-) (Fc = ferrocenyl). W(CO) 5 ( E -2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine ( E -3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E -3 are performed by NMR, IR and UV-vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO) 5 ( E -2) decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG (‡) 298K = 112 kJ mol(-1). Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent) densitiy functional theory [(TD)-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II) intermediates cis (N,H)-W(CO) 4 (H)( Z -15) and cis (C,H)-W(CO) 4 (H)( Z -15).
- Date of acceptance
- 2016
- Autoren
- Philipp Veit
- Christoph Förster
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/27559381
- DOI
- 10.3762/bjoc.12.125
- Externe Identifier
- PubMed Central ID: PMC4979739
- ISSN
- 1860-5397
- Zeitschrift
- Beilstein J Org Chem
- Schlüsselwörter
- carbene complexes
- ferrocene
- imine
- mechanism
- tungsten
- Sprache
- eng
- Country
- Germany
- Paginierung
- 1322 - 1333
- Datum der Veröffentlichung
- 2016
- Status
- Published online
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2016
- Titel
- On the mechanism of imine elimination from Fischer tungsten carbene complexes.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 12
Data source: PubMed
- Beziehungen:
-