%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 = {2022-06-15T11:26:56.000+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/huebleriac}, 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 = {2022-06-15T09:26:56.000+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 }