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- W2329885539 abstract "On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(μ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(μ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(μ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination from the Ni(II) and Pt(II) centers. Oxidation occurs by removing one electron from this second multicenter molecular orbital. Although the mixed-valence character of the oxidized species makes the isolation of MM'X chains very attractive, such polymeric structure is prevented by the low Pt-Cl···Ni interaction energy and the high tendency of Ni centers to coordinate water molecules. Thus, this work offers valuable insights and hints to engage the production of heterometallic mixed-valence MM'X chains, which still is a challenging task." @default.
- W2329885539 created "2016-06-24" @default.
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- W2329885539 date "2014-09-19" @default.
- W2329885539 modified "2023-10-17" @default.
- W2329885539 title "On the Road to MM′X Polymers: Redox Properties of Heterometallic Ni···Pt Paddlewheel Complexes" @default.
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- W2329885539 doi "https://doi.org/10.1021/ic501659x" @default.
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