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Systematic tuning of the reactivity of [RuII(terpy)(N^N)Cl]Cl complexes

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The substitution behavior of the [RuII(terpy)(ampy)Cl]Cl (terpy = 2,2′:6′,2′′-terpyridine, ampy = 2-(aminomethyl)pyridine) complex in water with several bio-relevant ligands such as chloride, thiourea and N,N′-dimethylthiourea, was investigated and compared with the reactivity of the [RuII(terpy)(bipy)Cl]Cl and [RuII(terpy)(en)Cl]Cl (bipy =2,2′-bipyridine and en = ethylenediamine) complexes. Earlier results have shown that the reactivity and pK a values of Ru(II) complexes can be tuned by a systematic variation of electronic effects provided by bidentate spectator chelates. The reactivity of both the chlorido and aqua derivatives of the studied Ru(II) complexes increases in the order [RuII(terpy)(bipy)X]+/2+ < [RuII(terpy)(ampy)X]+/2+ < [RuII(terpy)(en)X]+/2+. This finding can be accounted for in terms of π back-bonding effects provided by the pyridine ligands. The activation parameters for all the studied reactions support an associative interchange substitution mechanism.
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Keywords: DFT calculations; Ru(II) complexes; aquation; electronic tuning effects; ligand substitution

Document Type: Research Article

Affiliations: 1: Faculty of Chemistry, N. Copernicus University, Toruń, Poland; 2: Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Erlangen, Germany;

Publication date: July 3, 2018

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