Controlling metal-ligand-metal oxidation state combinations by ancillary ligand (L) variation in the redox systems L2Ru(m-boptz)RuL2n, boptz = 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine(2-), and L = acetylacetonate, 2,2'-bipyridine, or 2-phenylazopyridine
(Acac)2Ru(m-boptz)Ru(acac)2 (1), (bpy)2Ru(m-boptz)Ru(bpy)2(ClO4)2 (2-(ClO4)2), and (pap)2Ru(m-boptz)Ru(pap)2(ClO4)2 (3-(ClO4)2) were obtained from 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz), the crystal structure anal. of which is reported. Compd. 1 contains two antiferromagnetically coupled (J = -36.7 cm-1) RuIII centers. The authors have studied the role of both the donor and acceptor functions contg. the boptz2- bridging ligand in combination with the electronically different ancillary ligands (donating acac-, moderately p-accepting bpy, and strongly p-accepting pap (2-phenylazopyridine)) by using cyclic voltammetry, spectroelectrochem. and EPR spectroscopy for several in situ accessible redox states. Metal-ligand-metal oxidn. state combinations remain invariant to ancillary ligand change in some instances; however, three isoelectronic paramagnetic cores Ru(m-boptz)Ru showed remarkable differences. The excellent tolerance of the bpy coligand for both RuIII and RuII is demonstrated by the adoption of the mixed-valent form in L2Ru(m-boptz)RuL23+, L = bpy, whereas the corresponding system with pap stabilizes the RuIII states to yield a phenoxyl radical ligand and the compd. with L = acac- contains two RuIII centers connected by a tetrazine radical-anion bridge. on SciFinder(R)
%0 Journal Article
%1 Patra.2006
%A Patra, Srikanta
%A Sarkar, Biprajit
%A Maji, Somnath
%A Fiedler, Jan
%A Urbanos, Francisco A.
%A Jimenez-Aparicio, Reyes
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar.
%D 2006
%J Chemistry - A European Journal
%K acetylacetonate antiferromagnetic azopyridine bipyridine complex complex;charge complex;crystal complex;hydroxyphenyltetrazine complexation dinuclear exchange hydroxyphenyltetrazine hydroxyphenyltetrazine;electrochem prepn redox ruthenium ruthenium;ruthenium spectra structure transfer
%N 2
%P 489--498
%R 10.1002/chem.200500295
%T Controlling metal-ligand-metal oxidation state combinations by ancillary ligand (L) variation in the redox systems L2Ru(m-boptz)RuL2n, boptz = 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine(2-), and L = acetylacetonate, 2,2'-bipyridine, or 2-phenylazopyridine
%V 12
%X (Acac)2Ru(m-boptz)Ru(acac)2 (1), (bpy)2Ru(m-boptz)Ru(bpy)2(ClO4)2 (2-(ClO4)2), and (pap)2Ru(m-boptz)Ru(pap)2(ClO4)2 (3-(ClO4)2) were obtained from 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz), the crystal structure anal. of which is reported. Compd. 1 contains two antiferromagnetically coupled (J = -36.7 cm-1) RuIII centers. The authors have studied the role of both the donor and acceptor functions contg. the boptz2- bridging ligand in combination with the electronically different ancillary ligands (donating acac-, moderately p-accepting bpy, and strongly p-accepting pap (2-phenylazopyridine)) by using cyclic voltammetry, spectroelectrochem. and EPR spectroscopy for several in situ accessible redox states. Metal-ligand-metal oxidn. state combinations remain invariant to ancillary ligand change in some instances; however, three isoelectronic paramagnetic cores Ru(m-boptz)Ru showed remarkable differences. The excellent tolerance of the bpy coligand for both RuIII and RuII is demonstrated by the adoption of the mixed-valent form in L2Ru(m-boptz)RuL23+, L = bpy, whereas the corresponding system with pap stabilizes the RuIII states to yield a phenoxyl radical ligand and the compd. with L = acac- contains two RuIII centers connected by a tetrazine radical-anion bridge. on SciFinder(R)
@article{Patra.2006,
abstract = {[(Acac)2Ru(\textgreek{m}-boptz)Ru(acac)2] (1), [(bpy)2Ru(\textgreek{m}-boptz)Ru(bpy)2](ClO4)2 (2-(ClO4)2), and [(pap)2Ru(\textgreek{m}-boptz)Ru(pap)2](ClO4)2 (3-(ClO4)2) were obtained from 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz), the crystal structure anal. of which is reported. Compd. 1 contains two antiferromagnetically coupled (J = -36.7 cm-1) RuIII centers. The authors have studied the role of both the donor and acceptor functions contg. the boptz2- bridging ligand in combination with the electronically different ancillary ligands (donating acac-, moderately \textgreek{p}-accepting bpy, and strongly \textgreek{p}-accepting pap (2-phenylazopyridine)) by using cyclic voltammetry, spectroelectrochem. and EPR spectroscopy for several in situ accessible redox states. Metal-ligand-metal oxidn. state combinations remain invariant to ancillary ligand change in some instances; however, three isoelectronic paramagnetic cores Ru(\textgreek{m}-boptz)Ru showed remarkable differences. The excellent tolerance of the bpy coligand for both RuIII and RuII is demonstrated by the adoption of the mixed-valent form in [L2Ru(\textgreek{m}-boptz)RuL2]3+, L = bpy, whereas the corresponding system with pap stabilizes the RuIII states to yield a phenoxyl radical ligand and the compd. with L = acac- contains two RuIII centers connected by a tetrazine radical-anion bridge. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Patra, Srikanta and Sarkar, Biprajit and Maji, Somnath and Fiedler, Jan and Urbanos, Francisco A. and Jimenez-Aparicio, Reyes and Kaim, Wolfgang and Lahiri, Goutam Kumar.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2b4758ab6ec21a8cf43f3f3b2442cd0a3/b_schwederski},
doi = {10.1002/chem.200500295},
interhash = {44a8ddec4ab16ae085d4c1de480bdc61},
intrahash = {b4758ab6ec21a8cf43f3f3b2442cd0a3},
issn = {0947-6539},
journal = {Chemistry - A European Journal},
keywords = {acetylacetonate antiferromagnetic azopyridine bipyridine complex complex;charge complex;crystal complex;hydroxyphenyltetrazine complexation dinuclear exchange hydroxyphenyltetrazine hydroxyphenyltetrazine;electrochem prepn redox ruthenium ruthenium;ruthenium spectra structure transfer},
number = 2,
pages = {489--498},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Controlling metal-ligand-metal oxidation state combinations by ancillary ligand (L) variation in the redox systems [L2Ru(\textgreek{m}-boptz)RuL2]n, boptz = 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine(2-), and L = acetylacetonate, 2,2'-bipyridine, or 2-phenylazopyridine},
volume = 12,
year = 2006
}