2,4,6-Tris(2-pyridyl)-1,3,5-triazine (tptz)-derived [Ru(II)(tptz)(acac)(CH3CN)]+ and mixed-valent [(acac)2Ru(III){(mu-tptz-H+)-}Ru(II)(acac)(CH3CN)]+

Inorganic Chemistry
Sandeep GhumaanGoutam Kumar Lahiri

Abstract

Mononuclear [Ru(II)(tptz)(acac)(CH3CN)]ClO4 ([1]ClO4) and mixed-valent dinuclear [(acac)2Ru(III){(mu-tptz-Eta+)-}Ru(II)(acac)(CH3CN)]ClO4 ([5]ClO4; acac = acetylacetonate) complexes have been synthesized via the reactions of Ru(II)(acac)2(CH3CN)2 and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), in 1:1 and 2:1 molar ratios, respectively. In [1]ClO4, tptz binds with the Ru(II) ion in a tridentate N,N,N mode (motif A), whereas in [5]ClO4, tptz bridges the metal ions unsymmetrically via the tridentate neutral N,N,N mode with the Ru(II) center and cyclometalated N,C- state with the Ru(III) site (motif F). The activation of the coordinated nitrile function in [1]ClO4 and [5]ClO4 in the presence of ethanol and alkylamine leads to the formation of iminoester ([2]ClO4 and [7]ClO4) and amidine ([4]ClO4) derivatives, respectively. Crystal structure analysis of [2]ClO4 reveals the formation of a beautiful eight-membered water cluster having a chair conformation. The cluster is H-bonded to the pendant pyridyl ring N of tptz and also with the O atom of the perchlorate ion, which, in turn, makes short (C-H- - - - -O) contacts with the neighboring molecule, leading to a H-bonding network. The redox potentials corresponding to the Ru(II) state ...Continue Reading

References

Apr 16, 2002·Inorganic Chemistry·Nadezhda A BokachArmando J L Pombeiro
Aug 15, 2002·Chemical Reviews·Teresa Head-Gordon, Greg Hura
Jul 10, 2003·Chemical Reviews·Frank N KeutschRichard J Saykally
Oct 27, 2004·Inorganic Chemistry·Sujit K Ghosh, Parimal K Bharadwaj

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Citations

Sep 6, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Takuya ShigaHiroki Oshio
Aug 1, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Albrecht BerkesselBiprajit Sarkar
May 15, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthias SchwalbeSven Rau
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Goutam Kumar Lahiri, Wolfgang Kaim
Aug 15, 2019·Chemistry : a European Journal·Debarpan DuttaPrasanta Ghosh
Apr 1, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Derek J ReidJennifer Scott

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