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Reduced and Superreduced Diplatinum Complexes.

Tania V Darnton¹, Bryan M Hunter¹, Michael G Hill²

¹Beckman Institute, California Institute of Technology , Pasadena, California 91125, United States.

Journal of the American Chemical Society

|April 13, 2016

Summary

This summary is machine-generated.

The study shows that reducing a platinum complex strengthens platinum-platinum bonds and makes it a potent photooxidant. This research explores electron transfer in binuclear platinum complexes.

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Area of Science:

Inorganic Chemistry
Electrochemistry
Photochemistry

Background:

Binuclear platinum complexes with d(8)-d(8) configurations are of interest for their electronic properties.
Understanding electron transfer processes is crucial for designing novel functional materials.

Purpose of the Study:

To investigate the electrochemical reduction of the d(8)-d(8) platinum complex [Pt2(μ-P2O5(BF2)4](4-) (Pt(pop-BF2)(4-)).
To characterize the electronic structure and bonding changes upon reduction.
To evaluate the photooxidant properties of the parent and reduced species.

Main Methods:

Electrochemical techniques (cyclic voltammetry) to study reduction potentials.
Electron Paramagnetic Resonance (EPR) spectroscopy to analyze the reduced species.
UV-vis spectroscopy and Time-Dependent Density Functional Theory (TD-DFT) calculations for electronic structure.
Mayer-Millikan bond order calculations to quantify Pt-Pt bonding.

Main Results:

Two one-electron reductions were observed at -1.68 V and -2.46 V, forming Pt(pop-BF2)(5-) and Pt(pop-BF2)(6-).
Reductions involve filling of the 6pσ orbital, strengthening Pt-Pt and Pt-P bonds.
Pt-Pt bond order increased from 0.173 to 0.340 upon reduction.
The superreduced Pt(pop-BF2)(6-) is a rare 6p(2) σ-bonded binuclear complex, though Pt-Pt distance is limited.
The parent complex is predicted to be a strong photooxidant with excited state potentials of +1.57 V (singlet) and +0.86 V (triplet).

Conclusions:

The study elucidates the electronic and structural consequences of stepwise reduction in a binuclear platinum complex.
The findings highlight the potential of such complexes as strong photooxidants.
The research contributes to understanding bonding in electron-rich, multi-metallic systems.