Ruthenium(II) as a novel "labile" partner in thermodynamic self-assembly of heterobimetallic d-f triple-stranded helicates

Chemistry : a European Journal
Stéphane TorelliClaude Piguet

Abstract

Unsymmetrical substituted bidentate benzimidazol-2-ylpyridine ligands L2 and L3 react with [Ru(dmso)(4)Cl(2)] in ethanol to give statistical 1:3 mixtures of fac-[Ru(Li)(3)](2+) and mer-[Ru(Li)(3)](2+) (i=2, 3; DeltaGtheta(isomerisation)=-2.7 kJ mol(-1)). In more polar solvents (acetonitrile, methanol), the free energy of the facial<=>meridional isomerisation process favours mer-[Ru(Li)(3)](2+), which is the only isomer observed in solution at the equilibrium (DeltaGtheta(isomerisation)< or = -11.4 kJ mol(-1)). Since the latter process takes several days for [Ru(L2)(3)](2+), fac-[Ru(L2)(3)](2+) and mer-[Ru(L2)(3)](2+) have been separated by chromatography, but the 28-fold increase in velocity observed for [Ru(L3)(3)](2+) provides only mer-[Ru(L3)3](ClO(4))2 after chromatography (RuC(60)H(51)N(9)O(8)Cl(2), monoclinic, P2(1)/n, Z=4). The facial isomer can be stabilised when an appended tridentate binding unit, connected at the 5-position of the benzimidazol-2-ylpyridine unit in ligand L1, interacts with nine-coordinate lanthanides(III). The free energy of the facial<=>meridional isomerisation is reversed (DeltaGtheta(isomerisation)> or =11.4 kJ mol(-1)), and the Ru--N bonds are labile enough to allow the quantitative thermodynamic...Continue Reading

Citations

Mar 19, 2016·Inorganic Chemistry·Anastasia B S ElliottKeith C Gordon
Jan 21, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Serin L Dabb, Nicholas C Fletcher
Aug 22, 2014·Nature Chemistry·Alan D FaulknerPeter Scott
Jan 25, 2007·Chemistry : a European Journal·David Schultz, Jonathan R Nitschke
Oct 31, 2008·Chemistry : a European Journal·Christopher R K GlassonCherie Motti
Mar 19, 2009·Chemical Communications : Chem Comm·Suzanne E HowsonPeter Scott
Oct 22, 2009·Chemistry : a European Journal·Thomas Riis-JohannessenClaude Piguet
Aug 18, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiao-Yan LiKe Wen
Mar 7, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Dusan DrahonovskýAlex von Zelewsky
Jan 29, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Naomi C A BakerMichael B Hursthouse
Jul 12, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Suzanne E HowsonPeter Scott
Jul 15, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Gareth CookeSylvia M Draper
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Feb 16, 2010·Chemical Reviews·Jean-Claude G Bünzli
Nov 20, 2014·Inorganic Chemistry·Lilit Aboshyan-SorghoClaude Piguet
Jun 24, 2014·Inorganic Chemistry·Takayuki NakanishiYasuchika Hasegawa
Aug 2, 2006·Inorganic Chemistry·Nicholas C FletcherAndrew P Doherty

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