Photolytic Activation of Late-Transition-Metal–Carbon Bonds and Their Reactivity toward Oxygen
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https://figshare.com/articles/dataset/Photolytic_Activation_of_Late-Transition-Metal_Carbon_Bonds_and_Their_Reactivity_toward_Oxygen/17147746
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资源简介：
The photolytic activation of palladium(II)
and platinum(II) complexes
[M(BPI)(R)] (R = alkyl, aryl) featuring the 1,3-bis(2-pyridylimino)isoindole
(BPI) ligand has been investigated in various solvents.
In the absence of oxygen, the formation of chloro complexes [M(BPI)Cl] is observed in chlorinated solvents, most likely due
to the photolytic degradation of the solvent and formation of HCl.
The reactivity of the complexes toward oxygen has been studied both
experimentally and computationally. Excitation by UV irradiation (365
nm) of the metal complexes [Pt(BPI)Me] and [Pd(BPI)Me] leads to distortion of the square-planar coordination
geometry in the excited triplet state and a change in the electronic
structure of the complexes that allows the interaction with oxygen.
TD-DFT computational studies suggest that, in the case of palladium,
the Pd(III) superoxide intermediate [Pd(BPI)(κ1-O2)Me] is formed and, in the case of platinum,
the Pt(IV) peroxide intermediate [Pt(BPI)(κ2-O2)Me]. For alkyl complexes where metal–carbon
bonds are sufficiently weak, the photoactivation leads to the insertion
of oxygen into the metal–carbon bond to generate alkylperoxo
complexes: for example [Pd(BPI)OOMe], which has been
isolated and structurally characterized. For stronger M–C(aryl)
bonds, the reaction of [Pt(BPI)Ph] with O2 and light results in a Pt(IV) complex, tentatively assigned as the
peroxo complex [Pt(BPI)(κ2-O2)Ph], which in chlorinated solvents reacts further to give [Pt(BPI)Cl2Ph], which has been isolated and characterized
by scXRD. In addition to the facilitation of oxygen insertion reactions,
UV irradiation can also affect the reactivity of other components
in the reaction mixture, such as the solvent or other reaction products,
which can result in further reactions. Labeling studies using [Pt(BPI)(CD3)] in chloroform have shown that photolytic
reactions with oxygen involve degradation of the solvent.
创建时间：
2021-12-08
