Magnesium-stabilised transition metal formyl complexes: structures, bonding, and ethenediolate formation.
Journal
Chemical science
ISSN: 2041-6520
Titre abrégé: Chem Sci
Pays: England
ID NLM: 101545951
Informations de publication
Date de publication:
07 Jun 2022
07 Jun 2022
Historique:
received:
10
04
2022
accepted:
15
05
2022
entrez:
27
6
2022
pubmed:
28
6
2022
medline:
28
6
2022
Statut:
epublish
Résumé
Herein we report the first comprehensive series of crystallographically characterised transition metal formyl complexes. In these complexes, the formyl ligand is trapped as part of a chelating structure between a transition metal (Cr, Mn, Fe, Co, Rh, W, and Ir) and a magnesium (Mg) cation. Calculations suggest that this bonding mode results in significant oxycarbene-character of the formyl ligand. Further reaction of a heterometallic Cr-Mg formyl complex results in a rare example of C-C coupling and formation of an ethenediolate complex. DFT calculations support a key role for the formyl-intermediate in ethenediolate formation. These results show that well-defined transition metal formyl complexes are potential intermediates in the homologation of carbon monoxide.
Identifiants
pubmed: 35756511
doi: 10.1039/d2sc02063g
pii: d2sc02063g
pmc: PMC9172563
doi:
Types de publication
Journal Article
Langues
eng
Pagination
6592-6598Informations de copyright
This journal is © The Royal Society of Chemistry.
Déclaration de conflit d'intérêts
There are no conflicts to declare.
Références
Angew Chem Int Ed Engl. 2016 Jun 6;55(24):6951-3
pubmed: 27071992
Phys Chem Chem Phys. 2008 Nov 28;10(44):6615-20
pubmed: 18989472
Angew Chem Int Ed Engl. 2017 Nov 20;56(47):15127-15130
pubmed: 28975704
Angew Chem Int Ed Engl. 2008;47(28):5253-5
pubmed: 18528839
J Am Chem Soc. 2007 Mar 7;129(9):2529-41
pubmed: 17286402
J Chem Phys. 2008 Feb 28;128(8):084106
pubmed: 18315032
Science. 2006 Jan 27;311(5760):484-9
pubmed: 16439654
Nature. 2019 Oct;574(7778):390-393
pubmed: 31597960
Angew Chem Int Ed Engl. 1999 Aug;38(15):2233-2237
pubmed: 10425494
J Am Chem Soc. 2015 Jul 22;137(28):8944-7
pubmed: 26135846
Angew Chem Int Ed Engl. 2021 Mar 8;60(11):6145-6153
pubmed: 33275830