On the road to MM′X polymers: Redox properties of heterometallic Ni···Pt paddlewheel complexes

Marcello Gennari, Gonzalo Givaja, Oscar Castillo, Laura Hermosilla, Carlos J. Gómez-García, Carole Duboc, Agustí Lledós, Ruben Mas-Ballesté, Felix Zamora

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© 2014 American Chemical Society. On the quest of heterometallic mixed-valence MM′X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(Î-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(Î-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(Î-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 dx2-y2 orbital of the Ni(II) ion and a second in the antibonding dz2-dz2 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.
Idioma originalEnglish
Pàgines (de-a)10553-10562
RevistaInorganic Chemistry
Volum53
Número19
DOIs
Estat de la publicacióPublicada - 6 d’oct. 2014

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