Productive Alkyne Metathesis with "Canopy Catalysts" Mandates Pseudorotation.
Journal
Journal of the American Chemical Society
ISSN: 1520-5126
Titre abrégé: J Am Chem Soc
Pays: United States
ID NLM: 7503056
Informations de publication
Date de publication:
21 04 2021
21 04 2021
Historique:
pubmed:
8
4
2021
medline:
28
9
2021
entrez:
7
4
2021
Statut:
ppublish
Résumé
Molybdenum alkylidyne complexes of the "canopy catalyst" series define new standards in the field of alkyne metathesis. The tripodal ligand framework lowers the symmetry of the metallacyclobutadiene complex formed by [2 + 2] cycloaddition with the substrate and imposes constraints onto the productive [2 + 2] cycloreversion; pseudorotation corrects this handicap and makes catalytic turnover possible. A combined spectroscopic, crystallographic, and computational study provides insights into this unorthodox mechanism and uncovers the role that metallatetrahedrane complexes play in certain cases.
Identifiants
pubmed: 33826335
doi: 10.1021/jacs.1c01404
pmc: PMC8154524
doi:
Substances chimiques
Alkynes
0
Coordination Complexes
0
Molybdenum
81AH48963U
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
5643-5648Références
J Am Chem Soc. 2010 Aug 18;132(32):11045-57
pubmed: 20698671
J Am Chem Soc. 2017 Dec 6;139(48):17597-17607
pubmed: 29083916
Chemistry. 2019 Mar 1;25(13):3190-3208
pubmed: 30346054
Chemistry. 2012 Aug 13;18(33):10281-99
pubmed: 22807024
Angew Chem Int Ed Engl. 2007;46(46):8890-4
pubmed: 17935104
Chemistry. 2009;15(3):585-8
pubmed: 19065697
Angew Chem Int Ed Engl. 2020 Nov 23;59(48):21758-21768
pubmed: 32820864
Chem Asian J. 2018 Apr 16;13(8):895-912
pubmed: 29571217
Angew Chem Int Ed Engl. 2013 Mar 4;52(10):2794-819
pubmed: 23355479
Chemistry. 2016 Jun 13;22(25):8494-507
pubmed: 27203803
Angew Chem Int Ed Engl. 2019 Oct 28;58(44):15690-15696
pubmed: 31449713
J Am Chem Soc. 2020 Aug 5;142(31):13339-13344
pubmed: 32673485
J Am Chem Soc. 2020 Jun 24;142(25):11279-11294
pubmed: 32463684
Chem Commun (Camb). 2005 May 14;(18):2307-20
pubmed: 15877114