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         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/285037b5699fc4d95fb243b6f4e00bb97/huebleriac",         
         "tags" : [
            "azodicarbonyl","complex","complex;electron","complex;mixed","complex;substituent","configuration","dinuclear","effect","electrochem","ruthenium","valence"
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         "intraHash" : "85037b5699fc4d95fb243b6f4e00bb97",
         "interHash" : "25714849b0526cc5cc087918a8ef7ff4",
         "label" : "When Is an Odd-Electron Dinuclear Complex a Mixed-Valent Species? Tuning of Ligand-to-Metal Spin Shifts in Diruthenium(III,II) Complexes of Noninnocent Bridging Ligands OC(R)NNC(R)O",
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         "journal": "Inorganic Chemistry",
         "year": "1995", 
         "url": "", 
         
         "author": [ 
            "Volker Kasack","Wolfgang Kaim","Herbert Binder","Jeanne Jordanov","Eberhard. Roth"
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            	{"first" : "Volker",	"last" : "Kasack"},
            	{"first" : "Wolfgang",	"last" : "Kaim"},
            	{"first" : "Herbert",	"last" : "Binder"},
            	{"first" : "Jeanne",	"last" : "Jordanov"},
            	{"first" : "Eberhard.",	"last" : "Roth"}
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         "volume": "34","number": "7","pages": "1924--1933","abstract": "(Adc-R)[Ru(bpy)2]2n with bpy = 2,2'-bipyridine and adc-R = azodicarbonyl ligands O:C(R)N:NC(R):O, R = NR'2 (piperidyl), OEt, OCH2Ph, Me, Ph, 4-C6H4COOH, and 4-C6H4COOMe, can exist in several oxidn. states (n = 2-, 0, 2+, 3+, 4+) of which the stable (comproportionation const. Kc \\textgreater 5 $\\times$ 107) and isolable paramagnetic intermediates (n = 3+) exhibit a considerable and remarkably tunable degree of metal/ligand/metal orbital mixing.  The occurrence of intense (e \\textgreater 7000 M-1 cm-1) and small solvatochromic absorption bands at $\\sim$1500 nm, the temp.-dependent magnetic moment (meff = 1.6-2.1 mB) detd. for one deriv., and the IR vibrational spectra did not allow one to make a conclusive detn. of metal oxidn. states; however, the EPR spectra observable only \\textless50 K reveal a strongly substituent- (R-) dependent degree of metal contribution to the singly occupied MO.  XPS measurements of two 3+ ions which show Ru(II) and Ru(III) signals also exhibit a marked substituent effect on the electronic structure.  Whereas the 4+ ions formed at rather pos. potentials also seem to possess strongly mixed frontier orbitals, the stable 2+ ions clearly contain two Ru(II) centers and fully reduced, i.e. 1,2-dicarbonylhydrazido(2-), bridging ligands, [O:C(R)-N-N-C(R):O]2-.  The results are interpreted within a hole vs. electron transfer scheme, based on a three-site MO model for the metal/metal communication in ligand-bridged mixed-valent dimers according to which the intermediates (adc-R)[Ru(bpy)2]23+ are best described as delocalized systems with varying contributions from RuII/(adc-R).bul.-/RuII and RuII/(adc-R)2-/RuIII resonance forms. [on SciFinder(R)]",
         "issn" : "0020-1669",
         
         "doi" : "10.1021/ic00111a045",
         
         "bibtexKey": "Kasack.1995"

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         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/285037b5699fc4d95fb243b6f4e00bb97/b_schwederski",         
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            "azodicarbonyl","complex","complex;electron","complex;mixed","complex;substituent","configuration","dinuclear","effect","electrochem","ruthenium","valence"
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         "intraHash" : "85037b5699fc4d95fb243b6f4e00bb97",
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         "label" : "When Is an Odd-Electron Dinuclear Complex a Mixed-Valent Species? Tuning of Ligand-to-Metal Spin Shifts in Diruthenium(III,II) Complexes of Noninnocent Bridging Ligands OC(R)NNC(R)O",
         "user" : "b_schwederski",
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         "date" : "2019-07-15 13:41:23",
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         "pub-type": "article",
         "journal": "Inorganic Chemistry",
         "year": "1995", 
         "url": "", 
         
         "author": [ 
            "Volker Kasack","Wolfgang Kaim","Herbert Binder","Jeanne Jordanov","Eberhard. Roth"
         ],
         "authors": [
         	
            	{"first" : "Volker",	"last" : "Kasack"},
            	{"first" : "Wolfgang",	"last" : "Kaim"},
            	{"first" : "Herbert",	"last" : "Binder"},
            	{"first" : "Jeanne",	"last" : "Jordanov"},
            	{"first" : "Eberhard.",	"last" : "Roth"}
         ],
         "volume": "34","number": "7","pages": "1924--1933","abstract": "(Adc-R)[Ru(bpy)2]2n with bpy = 2,2'-bipyridine and adc-R = azodicarbonyl ligands O:C(R)N:NC(R):O, R = NR'2 (piperidyl), OEt, OCH2Ph, Me, Ph, 4-C6H4COOH, and 4-C6H4COOMe, can exist in several oxidn. states (n = 2-, 0, 2+, 3+, 4+) of which the stable (comproportionation const. Kc \\textgreater 5 $\\times$ 107) and isolable paramagnetic intermediates (n = 3+) exhibit a considerable and remarkably tunable degree of metal/ligand/metal orbital mixing.  The occurrence of intense (e \\textgreater 7000 M-1 cm-1) and small solvatochromic absorption bands at $\\sim$1500 nm, the temp.-dependent magnetic moment (meff = 1.6-2.1 mB) detd. for one deriv., and the IR vibrational spectra did not allow one to make a conclusive detn. of metal oxidn. states; however, the EPR spectra observable only \\textless50 K reveal a strongly substituent- (R-) dependent degree of metal contribution to the singly occupied MO.  XPS measurements of two 3+ ions which show Ru(II) and Ru(III) signals also exhibit a marked substituent effect on the electronic structure.  Whereas the 4+ ions formed at rather pos. potentials also seem to possess strongly mixed frontier orbitals, the stable 2+ ions clearly contain two Ru(II) centers and fully reduced, i.e. 1,2-dicarbonylhydrazido(2-), bridging ligands, [O:C(R)-N-N-C(R):O]2-.  The results are interpreted within a hole vs. electron transfer scheme, based on a three-site MO model for the metal/metal communication in ligand-bridged mixed-valent dimers according to which the intermediates (adc-R)[Ru(bpy)2]23+ are best described as delocalized systems with varying contributions from RuII/(adc-R).bul.-/RuII and RuII/(adc-R)2-/RuIII resonance forms. [on SciFinder(R)]",
         "issn" : "0020-1669",
         
         "doi" : "10.1021/ic00111a045",
         
         "bibtexKey": "Kasack.1995"

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