Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates

Powers, Dennis A.; Chambers, Matthew B.; Teets, Thomas S.; Elgrishi, Noémie; Anderson, Bo; Nocera, Daniel G.

doi:10.1039/c3sc50462j

Cited by 36 publications

(50 citation statements)

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“…Moreover, the current study provides an impetus for probing the biological properties of other multicenter inorganic complexes, since the same strategy can be used to label diruthenium 28 and dirhenium 29 anticancer compounds. It is worth pointing out that the realization that Rh–Rh bonded compounds can be successfully tagged with light-harvesting units such as bodipy will positively impact other research areas, such as the use of dirhodium compounds as photocatalysts, 30 − 32 since attaching a moiety with a high molar absorptivity to the dimetal core is expected to improve the efficiency of such catalytic systems.…”

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confidence: 99%

Confocal Fluorescence Microscopy Studies of a Fluorophore-Labeled Dirhodium Compound: Visualizing Metal–Metal Bonded Molecules in Lung Cancer (A549) Cells

et al. 2014

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The new dirhodium compound [Rh2(μ-O2CCH3)2(η1-O2CCH3)(phenbodipy)(H2O)3][O2CCH3] (1), which incorporates a bodipy fluorescent tag, was prepared and studied by confocal fluorescence microscopy in human lung adenocarcinoma (A549) cells. It was determined that 1 localizes mainly in lysosomes and mitochondria with no apparent nuclear localization in the 1–100 μM range. These results support the conclusion that cellular organelles rather than the nucleus can be targeted by modification of the ligands bound to the Rh24+ core. This is the first study of a fluorophore-labeled metal–metal bonded compound, work that opens up new venues for the study of intracellular distribution of dinuclear transition metal anticancer complexes.

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confidence: 99%

Confocal Fluorescence Microscopy Studies of a Fluorophore-Labeled Dirhodium Compound: Visualizing Metal–Metal Bonded Molecules in Lung Cancer (A549) Cells

et al. 2014

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“…Single-crystal X-ray diffraction of the photoproduct confirmed a μ-Cl-Rh 2 geometry for 8 , similar to previously synthesized isocyanide supported Cl-bridged structures. 20 Solution-phase photolysis of trans - 7 in THF also led to the rapid conversion to 8 , as established by monitoring the reaction by UV–vis spectroscopy (Figure 6a).…”

Section: Resultsmentioning

confidence: 86%

“… 23 [Rh(cod)Cl] 2 and [Rh(CO) 2 Cl] 2 were obtained from Strem Chemicals and used without purification. Ligand tfepma, 24 Rh 2 [I,III] complex 1 , 20 and Rh 2 [II,II] complex 2 ( 25 ) were prepared as previously described.…”

Section: Methodsmentioning

confidence: 99%

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Photocrystallographic Observation of Halide-Bridged Intermediates in Halogen Photoeliminations

et al. 2014

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Polynuclear transition metal complexes, which frequently constitute the active sites of both biological and chemical catalysts, provide access to unique chemical transformations that are derived from metal–metal cooperation. Reductive elimination via ligand-bridged binuclear intermediates from bimetallic cores is one mechanism by which metals may cooperate during catalysis. We have established families of Rh2 complexes that participate in HX-splitting photocatalysis in which metal–metal cooperation is credited with the ability to achieve multielectron photochemical reactions in preference to single-electron transformations. Nanosecond-resolved transient absorption spectroscopy, steady-state photocrystallography, and computational modeling have allowed direct observation and characterization of Cl-bridged intermediates (intramolecular analogues of classical ligand-bridged intermediates in binuclear eliminations) in halogen elimination reactions. On the basis of these observations, a new class of Rh2 complexes, supported by CO ligands, has been prepared, allowing for the isolation and independent characterization of the proposed halide-bridged intermediates. Direct observation of halide-bridged structures establishes binuclear reductive elimination as a viable mechanism for photogenerating energetic bonds.

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“…This procedure has previously been validated by comparison with Toepler pump combustion analysis. 15 …”

Section: Methodsmentioning

confidence: 99%

Tandem redox mediator/Ni(ii) trihalide complex photocycle for hydrogen evolution from HCl

et al. 2015

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Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates

Cited by 36 publications

References 19 publications

Confocal Fluorescence Microscopy Studies of a Fluorophore-Labeled Dirhodium Compound: Visualizing Metal–Metal Bonded Molecules in Lung Cancer (A549) Cells

Confocal Fluorescence Microscopy Studies of a Fluorophore-Labeled Dirhodium Compound: Visualizing Metal–Metal Bonded Molecules in Lung Cancer (A549) Cells

Photocrystallographic Observation of Halide-Bridged Intermediates in Halogen Photoeliminations

Tandem redox mediator/Ni(ii) trihalide complex photocycle for hydrogen evolution from HCl

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