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- Title
The Role of Anionic Ligands on Photoreactivity in Mo(VI) Dioxo Complexes of the Form MoO<sub>2</sub>X<sub>2</sub>(NN).
- Authors
Fosshat, Saeed; Fronczek, Frank R.; Chambers, Matthew B.
- Abstract
The photoreactivity of d0 metal dioxo complexes in activating C--H bonds has been recently studied.[1-3] We have previously reported that MoO2X2(bpy-tBu) is an effective platform for light initiated C--H activation with unique product selectivity for the overall functionalization.[1] Herein we expand on these studies and report the synthesis and photoreactivity of several new Mo(VI) dioxo complexes with the general formula MoO2(X)2(NN); where X=F-, Cl-, Br-, CH3- PhO, tBuO- and NN=2,2'-bipyridine (bpy) or 4,4'-tert-butyl- 2,2'bipyridine (bpy-tBu). Among these compounds, MoO2Cl2(bpy-tBu) and MoO2Br2(bpy-tBu) are able to participate in bimolecular photoreactivity with several substrates containing C--H bonds of various types such as allyls, benzyls, aldehydes (RCHO) and alkanes. MoO2(CH3)2bpy and MoO2(PhO)2bpy do not participate in bimolecular photoreactions and instead they undergo photodecompositions. Computational studies indicate that the nature of the HOMO and LUMO is critical in supporting photoreactivity, with access to an LMCT (bpy→Mo) being necessary for tractable hydrocarbon functionalization.
- Subjects
LIGANDS (Chemistry); METAL complexes; PHOTOCHEMISTRY; COMPUTATIONAL chemistry; EXCITED states
- Publication
Chemistry - A European Journal, 2023, Vol 29, Issue 29, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202300486