CO‐Preserving Photoinduced Transfer of Cymantrenyl Moiety: a Tandem Experimental and Computational Investigation

Author:

Chaliy Vasiliy A.12ORCID,Kelbysheva Elena S.3ORCID,Ezernitskaya Mariam G.3ORCID,Strelkova Tatyana V.3ORCID,Bochenkova Anastasia V.4ORCID,Medvedev Michael G.13ORCID,Telegina Lyudmila N.3ORCID

Affiliation:

1. N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences Leninsky prospect 47 119991 Moscow Russian Federation

2. Higher Chemical College of the Russian Academy of Sciences D. Mendeleev University of Chemical Technology of Russia Miusskaya square 9 125047 Moscow Russian Federation

3. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Vavilova st. 28 119991 Moscow Russian Federation

4. Department of Chemistry Lomonosov Moscow State University Leninskie Gory 1/3 119991 Moscow Russian Federation

Abstract

AbstractCyclopentadienyl manganese tricarbonyl (cymantrene) is known to undergo photochemical reactions by releasing one of its CO ligands. Here we present the first example of a photorearrangement of a cymantrenylmethyl fragment, where it retains all its three CO ligands. A tandem experimental and DFT (density functional theory)‐based computational investigation allows us to explain this unexpected behavior: the rearrangement, indeed, begins with the release of one CO ligand, but cage effect of the solvent captures this CO molecule, allowing it to rapidly reattach once the rearrangement takes place.

Funder

Russian Science Foundation

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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