Journal ArticleDOI
Tuning the Electronic Communication in Heterobimetallic Mixed-Valence Ions of (1-Ferrocenyl)- and (2-Ferrocenyl)indenyl Rhodium Isomers
Saverio Santi,Laura Orian,Christian Durante,Annalisa Bisello,Franco Benetollo,Laura Crociani,Paolo Ganis,Alberto Ceccon +7 more
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TLDR
These methods allow us to establish a trend based on the magnitude of iron-rhodium electronic coupling H(ab) ranging from valence trapped to almost delocalised ions.Abstract:
A series of heterobimetallic complexes of general structure [RhL(2){eta(5)-(2-ferrocenyl)indenyl}] (L(2)=cod, nbd, L=CO; cod=cyclooctadiene; nbd=norbornadiene) has been synthesised with the aim of tuning the metal-metal interaction in their mixed-valence ions generated both by chemical and electrochemical oxidation, and the results are compared with those obtained for [RhL(2){eta(5)-(1-ferrocenyl)indenyl}] isomers. Crystallographic studies and DFT calculations provide a detailed description of the structural and electronic features of these complexes evidencing a significant difference in the extent of planarity of the flexible bridging ligand between the 1- and 2-ferrocenyl isomers. Independent experimental probes, in particular the potential splitting in the cyclic voltammograms and the IT bands in the near-IR spectra, are rationalised in the framework of Marcus-Hush theory and at quantum chemistry level by DFT and TD-DFT methods. These methods allow us to establish a trend based on the magnitude of iron-rhodium electronic coupling H(ab) ranging from valence trapped to almost delocalised ions. The quasi planar bridge and the olefin ancillary ligands make [Rh(nbd){eta(5)-(2-ferrocenyl)indenyl}](+) and [Rh(cod){eta(5)-(2-ferrocenyl)indenyl}](+) rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.read more
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Electronic communication through unsaturated hydrocarbon bridges in homobimetallic organometallic complexes.
Journal ArticleDOI
Charge Delocalization in a Heterobimetallic Ferrocene−(Vinyl)Ru(CO)Cl(PiPr3)2 System††Dedicated to Prof. Dr. Helmut Werner on the occasion of his 75th birthday
Konrad Kowalski,Michael Linseis,Rainer F. Winter,Manfred Zabel,Stanislav Záliš,Harald Kelm,Hans-Jörg Krüger,Biprajit Sarkar,Wolfgang Kaim +8 more
TL;DR: In this paper, the authors showed that the ferrocene and (vinyl)ruthenium redox sites of complex 1 undergo two consecutive reversible oxidations and showed a deformation of the Ru−C(CO) and Ru−P(V) bond upon oxidation.
Journal ArticleDOI
Optical, Magnetic, Electrochemical, and Electrical Properties of 8-Hydroxyquinoline-Based Complexes with Al3+, Cr3+, Mn2+, Co2+, Ni2+, Cu2+, and Zn2+
TL;DR: In this paper, the 8-hydroxyquinoline ligand was synthesized to investigate the effect of transition-metal ions on their electronic structure and electrical conductivity, and the results indicated that the π electrons localized on the ligands do not interact with the d electrons of the metal.
Journal ArticleDOI
Key multi(ferrocenyl) complexes in the interplay between electronic coupling and electrostatic interaction
TL;DR: The results are compared with the outcomes of some of the recent studies on conjugated ferrocenyl complexes to give an overview of how the nature of the bridging ligand, the distance between the redox-active centres, and the medium affect the electronic and electrostatic properties of the molecules.
Journal ArticleDOI
Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCp)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions.
Saverio Santi,Laura Orian,Christian Durante,Eva Zsuzsanna Bencze,Annalisa Bisello,Alessandro Donoli,Alberto Ceccon,Franco Benetollo,Laura Crociani +8 more
TL;DR: Despite their redox asymmetry, even in the heterobimetallic iron-rhodium as-indacenediide complexes, strong metal-metal coupling is present, in fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron r Rhodium site.
References
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P. Jeffrey Hay,Willard R. Wadt +1 more
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