Abstract
AbstractIn the search for a versatile building block that allows the preparation of heteroditopic tpy‐pincer bridging ligands, the synthon {4′‐[C6H3(CH2Br)2‐3,5]‐2,2′:6′,2″‐terpyridine} was synthesized. Facile introduction of diphenylphosphanyl groups in this synthon gave the ligand {4′‐[C6H3(CH2PPh2)2‐3,5]‐2,2′:6′,2″‐terpyridine} ([tpyPC(H)P]). The asymmetric mononuclear complex [Fe(tpy){tpyPC(H)P}](PF6)2, prepared by selective coordination of [Fe(tpy)Cl3] to the tpy moiety of [tpyPC(H)P], was used for the synthesis of the heterodimetallic complex [Fe(tpy)(tpyPCP)Ru(tpy)](PF6)3, which applies the “complex as ligand” approach. Coordination of the ruthenium centre at the PC(H)P‐pincer moiety of [Fe(tpy){tpyPC(H)P}](PF6)2 has been achieved by applying a transcyclometallation procedure. The ground‐state electronic properties of both complexes, investigated by cyclic and square‐wave voltammetries and UV/Vis spectroscopy, are discussed and compared with those of [Fe(tpy)2](PF6)2 and [Ru(PCP)(tpy)]Cl, which represent the mononuclear components of the heterodinuclear species. An in situ UV/Vis spectroelectrochemical study was performed in order to localize the oxidation and reduction steps and to gain information about the FeII–RuII communication in the heterodimetallic system [Fe(tpy)(tpyPCP)Ru(tpy)](PF6)3 mediated by the bridging ligand [tpyPCP]. Both the voltammetric and spectroelectrochemical results point to only very limited electronic interaction between the metal centres in the ground state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Published Version
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