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         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/2749b81ca5cbb600a1eaf5a100b0e9d5f/huebleriac",         
         "tags" : [
            "alkylation","calcn","complex","complex;spectroelectrochem","crystal","dipivaloylhydrazido","effect","mol","osmium","prepn","protonation","ruthenium","structure","structure;electron","transfer"
         ],
         
         "intraHash" : "749b81ca5cbb600a1eaf5a100b0e9d5f",
         "interHash" : "9408374c2f25345678ce79d71fdf8514",
         "label" : "Metalloradical Compounds with 1,2-Dipivaloylhydrazido Ligands: Electron Transfer and Alkylation/Protonation Effects",
         "user" : "huebleriac",
         "description" : "",
         "date" : "2022-06-15 11:26:56",
         "changeDate" : "2022-06-15 09:26:56",
         "count" : 3,
         "pub-type": "article",
         "journal": "European Journal of Inorganic Chemistry",
         "year": "2019", 
         "url": "", 
         
         "author": [ 
            "Sudipta Mondal","Vasileios Filippou","Martina Bubrin","Brigitte Schwederski","Jan Fiedler","Wolfgang. Kaim"
         ],
         "authors": [
         	
            	{"first" : "Sudipta",	"last" : "Mondal"},
            	{"first" : "Vasileios",	"last" : "Filippou"},
            	{"first" : "Martina",	"last" : "Bubrin"},
            	{"first" : "Brigitte",	"last" : "Schwederski"},
            	{"first" : "Jan",	"last" : "Fiedler"},
            	{"first" : "Wolfgang.",	"last" : "Kaim"}
         ],
         "volume": "2019","number": "21","pages": "2639--2647","abstract": "Under oxidative conditions the complexes M(bpy)2Cl2, M = Ru or Os, react with 1,2-dipivaloylhydrazine H2L = tBuC(O)-NH-NH-C(O)-tBu to yield the paramagnetic compds. [M(L)(bpy)2](PF6) 1(PF6), M = Ru and 2(PF6), M = Os.  Crystal structures of 1(ClO4) and 2(PF6) reveal an NNCO chelate coordination of L with d(NN) $\\approx$ 1.39 \\AA.  EPR spectroscopy suggests a metal/ligand mixed situation for the unpaired electron, with 29 \\% (Ru, 1+) or 46 \\% (Os, 2+) metal spin contribution according to DFT calcns.  Both complex cations exhibit reversible one-electron oxidn. and redn. (Kc $\\approx$ 1019 for 1+ and 1012 for 2+) which could also be monitored by IR (nCO) and UV/Vis-NIR spectroelectrochem.  These data confirm a metal/ligand orbital mixing MII(L·-) $łeftrightarrow$ MIII(L2-), with the osmium analog favoring the latter alternative.  Reaction of Ru(bpy)2Cl2 under non-oxidizing conditions yields the intermediate (1H)(PF6) which could be oxidatively deprotonated to 1+ or methylated to (1Me)(PF6), both identified by 1H and 13C NMR.  While oxidn. of (1H)+ proceeds irreversibly due to proton loss, the reversible spectroelectrochem. oxidn. of (1Me)+ suggests a metal-based process RuII(LMe-) $\\rightarrow$ RuIII(LMe-).  The results reveal that not only dinuclear complexes of 1,2-diacylhydrazido ligands but also mononuclear analogs are distinguished by remarkably variable metal/ligand mixed contributions to the frontier orbitals. [on SciFinder(R)]",
         "issn" : "1434-1948",
         
         "doi" : "10.1002/ejic.201900391",
         
         "bibtexKey": "Mondal.2019"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/282951d10265eecfa5b6b21bfda53531e/huebleriac",         
         "tags" : [
            "axial","complex","effect","effect;spectroelectrochem","electrochem","ligand","ligation","nitrosyl","porphyrin","reaction","redox","ruthenium","study","tetraphenylporphyrin"
         ],
         
         "intraHash" : "82951d10265eecfa5b6b21bfda53531e",
         "interHash" : "8b4d411242b7805179b426464fa2163c",
         "label" : "Redox Properties of Ruthenium Nitrosyl Porphyrin Complexes with Different Axial Ligation: Structural, Spectroelectrochemical (IR, UV-Visible, and EPR), and Theoretical Studies",
         "user" : "huebleriac",
         "description" : "",
         "date" : "2022-06-15 11:26:56",
         "changeDate" : "2022-06-15 09:26:56",
         "count" : 3,
         "pub-type": "article",
         "journal": "Inorganic Chemistry",
         "year": "2008", 
         "url": "", 
         
         "author": [ 
            "Priti Singh","Atanu Kumar Das","Biprajit Sarkar","Mark Niemeyer","Federico Roncaroli","Jose A. Olabe","Jan Fiedler","Stanislav Zalis","Wolfgang. Kaim"
         ],
         "authors": [
         	
            	{"first" : "Priti",	"last" : "Singh"},
            	{"first" : "Atanu Kumar",	"last" : "Das"},
            	{"first" : "Biprajit",	"last" : "Sarkar"},
            	{"first" : "Mark",	"last" : "Niemeyer"},
            	{"first" : "Federico",	"last" : "Roncaroli"},
            	{"first" : "Jose A.",	"last" : "Olabe"},
            	{"first" : "Jan",	"last" : "Fiedler"},
            	{"first" : "Stanislav",	"last" : "Zalis"},
            	{"first" : "Wolfgang.",	"last" : "Kaim"}
         ],
         "volume": "47","number": "16","pages": "7106--7113","abstract": "Exptl. and computational results for different Ru nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1, 2, 3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1, 0)) are reported with respect to their electron-transfer behavior.  The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an MNO species with an almost-linear RuNO arrangement at 178.1(3)°.  [(Por)Ru(NO)(H2O)]BF4 undergoes 2 reversible 1-electron oxidn. processes.  Spectroelectrochem. measurements (IR, UV-visible-NIR, and EPR) indicate that the 1st oxidn. occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP.bul.- and 1290 cm-1 for TPP.bul.-), from the small shift of $\\sim$20 cm-1 for nNO and from the EPR signal at giso $\\approx$ 2.00.  The 2nd oxidn., which is electrochem. reversible for the OEP compd., shows a 55. cm-1 shift in nNO, suggesting a partially metal-centered process.  [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible 1-electron redn.  The site of the redn. was detd. by spectroelectrochem. studies to be NO-centered with a ca. -300 cm-1 shift in nNO.  The EPR response of the NO.bul. complexes was essentially unaffected by the variation in the substituted pyridines X.  DFT calcns. support the interpretation of the exptl. results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H2O or pyridines, is centered at the porphyrin p system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has $\\sim$50\\% p*(NO) character.  This confirms that the (1st) oxidn. of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring whereas the redn. of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin Ru(II) state throughout.  The 4\\% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex. [on SciFinder(R)]",
         "issn" : "0020-1669",
         
         "doi" : "10.1021/ic702371t",
         
         "bibtexKey": "Singh.2008b"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/2ffc8ac9ac6e5c7681f8e0ed77243b8c9/huebleriac",         
         "tags" : [
            "ESR","carbonyl","complex","complex;crystal","complex;mol","complex;ruthenium","conjugated","conjugation","effect","electrooxidn;spectroelectrochem","hexenyl","oxidn","phosphine","pi","potential","prepn","pyrenylethenyl","pyridine","ruthenium","spectra","structure","styryl","vinyl","vinylruthenium"
         ],
         
         "intraHash" : "ffc8ac9ac6e5c7681f8e0ed77243b8c9",
         "interHash" : "9784e4c65bc618f661506a3660a9a016",
         "label" : "Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistry",
         "user" : "huebleriac",
         "description" : "",
         "date" : "2022-06-15 11:26:56",
         "changeDate" : "2022-06-15 09:26:56",
         "count" : 3,
         "pub-type": "article",
         "journal": "Journal of the American Chemical Society",
         "year": "2008", 
         "url": "", 
         
         "author": [ 
            "Joerg Maurer","Michael Linseis","Biprajit Sarkar","Brigitte Schwederski","Mark Niemeyer","Wolfgang Kaim","Stanislav Zalis","Chris Anson","Manfred Zabel","Rainer F. Winter"
         ],
         "authors": [
         	
            	{"first" : "Joerg",	"last" : "Maurer"},
            	{"first" : "Michael",	"last" : "Linseis"},
            	{"first" : "Biprajit",	"last" : "Sarkar"},
            	{"first" : "Brigitte",	"last" : "Schwederski"},
            	{"first" : "Mark",	"last" : "Niemeyer"},
            	{"first" : "Wolfgang",	"last" : "Kaim"},
            	{"first" : "Stanislav",	"last" : "Zalis"},
            	{"first" : "Chris",	"last" : "Anson"},
            	{"first" : "Manfred",	"last" : "Zabel"},
            	{"first" : "Rainer F.",	"last" : "Winter"}
         ],
         "volume": "130","number": "1","pages": "259--268","abstract": "A series of vinylruthenium bis-phosphine five- and six-coordinated complexes with non-conjugated 1-hexenyl, conjugated styryl and pyrenylethenyl ligands were prepd.; the effects of conjugation of the arom. system with vinyl p-bond on oxidn. potential, stability of the oxidated species, ESR spectra and IR CO-stretching bands were systematically explored by IR-spectroelectrochem. and DFT calcns.  Hydrometalation of 1-hexyne, phenylacetylene and 1-ethynylpyrene affords the corresponding five-coordinated ruthenium complexes [(PR3)2Cl(CO)RuCH:CHR1] (1a-3a; R = Ph, R1 = Bu, Ph, 1-pyrenyl; 1c-3c; R = iPr, same R1) and their octahedral pyridine adducts [(PPh3)2Cl(CO)(4-EtO2CC5H4N-kN)RuCH:CHR1] (1b-3b; same R1).  Crystal structures of 1b, 1c, 3c and 3a·PPh3 and enynyl complex [Ru(CO)Cl(PPh3)2(h1:h2-nBuHC:CHC$\\equiv$CnBu)], the result of coupling of the hexenyl ligand of complex 1a with another mol. of 1-hexyne, are reported.  All vinyl complexes undergo a one-electron oxidn. at fairly low potentials and a second oxidn. at more pos. potentials.  Anodic half-wave or peak potentials show a progressive shift to lower values as p-conjugation within the vinyl ligand increases.  Carbonyl band shifts of the metal-bonded CO ligand upon monooxidn. are significantly smaller than is expected of a metal-centered oxidn. process and are further diminished as the vinyl CH:CH entity is incorporated into a more extended p-system.  ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the av. g-value from that of the free electron.  The vinyl ligands thus strongly contribute to or even dominate the anodic oxidn. processes.  This renders them a class of truly \\dqnon-innocent\\dq ligands in organometallic ruthenium chem.  Exptl. findings are fully supported by quantum chem. calcns.  The contribution of the vinyl ligand to the HOMO increases from 46\\% (Ru-vinyl delocalized) to 84\\% (vinyl dominated) as R changes from Bu to 1-pyrenyl. [on SciFinder(R)]",
         "issn" : "0002-7863",
         
         "doi" : "10.1021/ja075547t",
         
         "bibtexKey": "Maurer.2008"

      }
,
      {
         "type" : "Publication",
         "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"
         ],
         
         "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",
         "user" : "huebleriac",
         "description" : "",
         "date" : "2022-06-15 11:26:56",
         "changeDate" : "2022-06-15 09:26:56",
         "count" : 3,
         "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"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/210a7ec1ce460c7d38fc8afca0f6b70a8/huebleriac",         
         "tags" : [
            "ancillary","bridged","complex","complex;cyclic","complex;unsym","crystal","diamidoanthraquinone","dinuclear","diruthenium","effect","ligand","prepn","ruthenium","spectroelectrochem","structure","unsym","voltammetry"
         ],
         
         "intraHash" : "10a7ec1ce460c7d38fc8afca0f6b70a8",
         "interHash" : "b4e7f94b1c360e9f1155fd41ab150206",
         "label" : "Analysis of Redox Series of Unsymmetrical 1,4-Diamido-9,10-anthraquinone-Bridged Diruthenium Compounds",
         "user" : "huebleriac",
         "description" : "",
         "date" : "2022-06-15 11:26:56",
         "changeDate" : "2022-06-15 09:26:56",
         "count" : 4,
         "pub-type": "article",
         "journal": "Inorganic Chemistry",
         "year": "2016", 
         "url": "", 
         
         "author": [ 
            "Abhishek Mandal","Md Asmaul Hoque","Anita Grupp","Alexa Paretzki","Wolfgang Kaim","Goutam Kumar. Lahiri"
         ],
         "authors": [
         	
            	{"first" : "Abhishek",	"last" : "Mandal"},
            	{"first" : "Md Asmaul",	"last" : "Hoque"},
            	{"first" : "Anita",	"last" : "Grupp"},
            	{"first" : "Alexa",	"last" : "Paretzki"},
            	{"first" : "Wolfgang",	"last" : "Kaim"},
            	{"first" : "Goutam Kumar.",	"last" : "Lahiri"}
         ],
         "volume": "55","number": "5","pages": "2146--2156","abstract": "The unsym. diruthenium complexes [(bpy)2RuII(m-H2L2-)RuIII(acac)2]ClO4 ([3]ClO4), [(pap)2RuII(m-H2L2-)RuIII(acac)2]ClO4 ([4]ClO4), and [(bpy)2RuII(m-H2L2-)RuII(pap)2](ClO4)2 ([5](ClO4)2) were obtained by way of the mononuclear precursors [(bpy)2RuII(H3L-)]ClO4 ([1]ClO4) and [(pap)2RuII(H3L-)]ClO4 ([2]ClO4) (bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine, acac- = 2,4-pentanedionate, and H4L = 1,4-diamino-9,10-anthraquinone).  Structural characterization by single-crystal x-ray diffraction and magnetic resonance (NMR, EPR) were used to establish the oxidn. state situation in each of the isolated materials.  Cyclic voltammetry, EPR, and UV-visible-near-IR (UV-visible-NIR) spectroelectrochem. were used to analyze the multielectron transfer series of the potentially class I mixed-valent dinuclear compds., considering the redox activities of differently coordinated metals, of the noninnocent bridge and of the terminal ligands.  Comparison with sym. analogs [L'2Ru(m-H2L)RuL'2]n (L' = bpy, pap, or acac-) shows that the redox processes in the unsym. dinuclear compds. are not averaged, with respect to the corresponding sym. systems, because of intramol. charge rearrangements involving the metals, the noninnocent bridge, and the ancillary ligands. [on SciFinder(R)]",
         "issn" : "0020-1669",
         
         "doi" : "10.1021/acs.inorgchem.5b02541",
         
         "bibtexKey": "Mandal.2016"

      }
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      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/23022d0ef889737bdfeee3ee620ceb5f0/huebleriac",         
         "tags" : [
            "calcn","communication","complex","complex;frontier","complex;mixed","complex;solvent","complex;vinylferrocene","conjugation","crystal","effect","electronic","electrooxidn;mol","ethenylruthenium","ferrocenyl","mixed","orbital","oxidn","prepn","ruthenium","sigma","spectra","structure","valence"
         ],
         
         "intraHash" : "3022d0ef889737bdfeee3ee620ceb5f0",
         "interHash" : "20994018d1f362552dbbc54ec04c1a86",
         "label" : "Charge delocalization in a heterobimetallic ferrocene-(vinyl)Ru(CO)Cl(PiPr3)2 system",
         "user" : "huebleriac",
         "description" : "",
         "date" : "2022-06-15 11:26:56",
         "changeDate" : "2022-06-15 09:26:56",
         "count" : 3,
         "pub-type": "article",
         "journal": "Organometallics",
         "year": "2009", 
         "url": "", 
         
         "author": [ 
            "Konrad Kowalski","Michael Linseis","Rainer F. Winter","Manfred Zabel","Stanislav Zalis","Harald Kelm","Hans-Jorg Kruger","Biprajit Sarkar","Wolfgang. Kaim"
         ],
         "authors": [
         	
            	{"first" : "Konrad",	"last" : "Kowalski"},
            	{"first" : "Michael",	"last" : "Linseis"},
            	{"first" : "Rainer F.",	"last" : "Winter"},
            	{"first" : "Manfred",	"last" : "Zabel"},
            	{"first" : "Stanislav",	"last" : "Zalis"},
            	{"first" : "Harald",	"last" : "Kelm"},
            	{"first" : "Hans-Jorg",	"last" : "Kruger"},
            	{"first" : "Biprajit",	"last" : "Sarkar"},
            	{"first" : "Wolfgang.",	"last" : "Kaim"}
         ],
         "volume": "28","number": "14","pages": "4196--4209","abstract": "Ruthenium s-vinylferrocene electronically conjugated redox-active complex was prepd.; mixed-valence cationic states were explored by spectroelectrochem., IR, NIR, ESR spectra, and DFT calcns.  Addn. of ruthenium hydride [RuH(CO)Cl(iPr3)2] to ethynylferrocene gave s-vinylruthenium complex [Cl(CO)(PiPr3)2RuCH:CHFc] (1, Fc = ferrocenyl), which was characterized by NMR, IR, ESI-MS, and Moessbauer spectroscopy and by x-ray crystallog.  Complex 1 features conjoined ferrocene and (vinyl)ruthenium redox sites and undergoes two consecutive reversible oxidns.  Pure samples of cryst., monooxidized [1·+][PF6] were prepd. by chem. oxidn. of 1 with the ferrocenium hexafluorophosphate.  Structural comparison with 1 reveals an increase of Fe-C and Fe-Cp bond lengths and ring tilting of the Cp decks, as is typical of ferrocenium ions, but also a discernible lengthening of the Ru-C(CO) and Ru-P bonds and a shortening of the Ru-C(vinyl) bond upon oxidn.  This supports the general idea of charge delocalization over both redox sites in 1·+.  Band shifts of the charge-sensitive IR labels (n(CO) for Ru, n(C-H, Cp) for Fc), the rather small g-anisotropy in the ESR spectrum of 1·+, and the results of quantum chem. calcns. indicate that in soln. the pos. charge partly resides on the vinyl ruthenium moiety.  Comparison of IR shifts in the solid state and in soln. and the quadrupole splitting in the Moessbauer spectrum of powd. 1·+ point to a larger extent of charge localization on the ferrocenyl site in solid samples.  This is probably due to CH···F hydrogen bonding interactions between the cyclopentadienyl hydrogen atoms of the radical cations and the PF6- counterions.  Monooxidized 1·+ displays low-energy electronic absorption bands at 1370 and 2150 nm.  According to quantum chem. calcns., the underlying transitions are largely localized on the ferrocene part of the mol. with only little charge transfer into the vinyl ruthenium subunit.  The second oxidn. is more biased toward the (vinyl)ruthenium site. [on SciFinder(R)]",
         "issn" : "0276-7333",
         
         "doi" : "10.1021/om9002945",
         
         "bibtexKey": "Kowalski.2009"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/23022d0ef889737bdfeee3ee620ceb5f0/b_schwederski",         
         "tags" : [
            "calcn","communication","complex","complex;frontier","complex;mixed","complex;solvent","complex;vinylferrocene","conjugation","crystal","effect","electronic","electrooxidn;mol","ethenylruthenium","ferrocenyl","mixed","orbital","oxidn","prepn","ruthenium","sigma","spectra","structure","valence"
         ],
         
         "intraHash" : "3022d0ef889737bdfeee3ee620ceb5f0",
         "interHash" : "20994018d1f362552dbbc54ec04c1a86",
         "label" : "Charge delocalization in a heterobimetallic ferrocene-(vinyl)Ru(CO)Cl(PiPr3)2 system",
         "user" : "b_schwederski",
         "description" : "",
         "date" : "2019-07-15 13:41:23",
         "changeDate" : "2019-07-15 11:42:10",
         "count" : 3,
         "pub-type": "article",
         "journal": "Organometallics",
         "year": "2009", 
         "url": "", 
         
         "author": [ 
            "Konrad Kowalski","Michael Linseis","Rainer F. Winter","Manfred Zabel","Stanislav Zalis","Harald Kelm","Hans-Jorg Kruger","Biprajit Sarkar","Wolfgang. Kaim"
         ],
         "authors": [
         	
            	{"first" : "Konrad",	"last" : "Kowalski"},
            	{"first" : "Michael",	"last" : "Linseis"},
            	{"first" : "Rainer F.",	"last" : "Winter"},
            	{"first" : "Manfred",	"last" : "Zabel"},
            	{"first" : "Stanislav",	"last" : "Zalis"},
            	{"first" : "Harald",	"last" : "Kelm"},
            	{"first" : "Hans-Jorg",	"last" : "Kruger"},
            	{"first" : "Biprajit",	"last" : "Sarkar"},
            	{"first" : "Wolfgang.",	"last" : "Kaim"}
         ],
         "volume": "28","number": "14","pages": "4196--4209","abstract": "Ruthenium s-vinylferrocene electronically conjugated redox-active complex was prepd.; mixed-valence cationic states were explored by spectroelectrochem., IR, NIR, ESR spectra, and DFT calcns.  Addn. of ruthenium hydride [RuH(CO)Cl(iPr3)2] to ethynylferrocene gave s-vinylruthenium complex [Cl(CO)(PiPr3)2RuCH:CHFc] (1, Fc = ferrocenyl), which was characterized by NMR, IR, ESI-MS, and Moessbauer spectroscopy and by x-ray crystallog.  Complex 1 features conjoined ferrocene and (vinyl)ruthenium redox sites and undergoes two consecutive reversible oxidns.  Pure samples of cryst., monooxidized [1·+][PF6] were prepd. by chem. oxidn. of 1 with the ferrocenium hexafluorophosphate.  Structural comparison with 1 reveals an increase of Fe-C and Fe-Cp bond lengths and ring tilting of the Cp decks, as is typical of ferrocenium ions, but also a discernible lengthening of the Ru-C(CO) and Ru-P bonds and a shortening of the Ru-C(vinyl) bond upon oxidn.  This supports the general idea of charge delocalization over both redox sites in 1·+.  Band shifts of the charge-sensitive IR labels (n(CO) for Ru, n(C-H, Cp) for Fc), the rather small g-anisotropy in the ESR spectrum of 1·+, and the results of quantum chem. calcns. indicate that in soln. the pos. charge partly resides on the vinyl ruthenium moiety.  Comparison of IR shifts in the solid state and in soln. and the quadrupole splitting in the Moessbauer spectrum of powd. 1·+ point to a larger extent of charge localization on the ferrocenyl site in solid samples.  This is probably due to CH···F hydrogen bonding interactions between the cyclopentadienyl hydrogen atoms of the radical cations and the PF6- counterions.  Monooxidized 1·+ displays low-energy electronic absorption bands at 1370 and 2150 nm.  According to quantum chem. calcns., the underlying transitions are largely localized on the ferrocene part of the mol. with only little charge transfer into the vinyl ruthenium subunit.  The second oxidn. is more biased toward the (vinyl)ruthenium site. [on SciFinder(R)]",
         "issn" : "0276-7333",
         
         "doi" : "10.1021/om9002945",
         
         "bibtexKey": "Kowalski.2009"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/210a7ec1ce460c7d38fc8afca0f6b70a8/b_schwederski",         
         "tags" : [
            "ancillary","bridged","complex","complex;cyclic","complex;unsym","crystal","diamidoanthraquinone","dinuclear","diruthenium","effect","ligand","prepn","ruthenium","spectroelectrochem","structure","unsym","voltammetry"
         ],
         
         "intraHash" : "10a7ec1ce460c7d38fc8afca0f6b70a8",
         "interHash" : "b4e7f94b1c360e9f1155fd41ab150206",
         "label" : "Analysis of Redox Series of Unsymmetrical 1,4-Diamido-9,10-anthraquinone-Bridged Diruthenium Compounds",
         "user" : "b_schwederski",
         "description" : "",
         "date" : "2019-07-15 13:41:23",
         "changeDate" : "2019-07-15 11:42:10",
         "count" : 4,
         "pub-type": "article",
         "journal": "Inorganic Chemistry",
         "year": "2016", 
         "url": "", 
         
         "author": [ 
            "Abhishek Mandal","Md Asmaul Hoque","Anita Grupp","Alexa Paretzki","Wolfgang Kaim","Goutam Kumar. Lahiri"
         ],
         "authors": [
         	
            	{"first" : "Abhishek",	"last" : "Mandal"},
            	{"first" : "Md Asmaul",	"last" : "Hoque"},
            	{"first" : "Anita",	"last" : "Grupp"},
            	{"first" : "Alexa",	"last" : "Paretzki"},
            	{"first" : "Wolfgang",	"last" : "Kaim"},
            	{"first" : "Goutam Kumar.",	"last" : "Lahiri"}
         ],
         "volume": "55","number": "5","pages": "2146--2156","abstract": "The unsym. diruthenium complexes [(bpy)2RuII(m-H2L2-)RuIII(acac)2]ClO4 ([3]ClO4), [(pap)2RuII(m-H2L2-)RuIII(acac)2]ClO4 ([4]ClO4), and [(bpy)2RuII(m-H2L2-)RuII(pap)2](ClO4)2 ([5](ClO4)2) were obtained by way of the mononuclear precursors [(bpy)2RuII(H3L-)]ClO4 ([1]ClO4) and [(pap)2RuII(H3L-)]ClO4 ([2]ClO4) (bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine, acac- = 2,4-pentanedionate, and H4L = 1,4-diamino-9,10-anthraquinone).  Structural characterization by single-crystal x-ray diffraction and magnetic resonance (NMR, EPR) were used to establish the oxidn. state situation in each of the isolated materials.  Cyclic voltammetry, EPR, and UV-visible-near-IR (UV-visible-NIR) spectroelectrochem. were used to analyze the multielectron transfer series of the potentially class I mixed-valent dinuclear compds., considering the redox activities of differently coordinated metals, of the noninnocent bridge and of the terminal ligands.  Comparison with sym. analogs [L'2Ru(m-H2L)RuL'2]n (L' = bpy, pap, or acac-) shows that the redox processes in the unsym. dinuclear compds. are not averaged, with respect to the corresponding sym. systems, because of intramol. charge rearrangements involving the metals, the noninnocent bridge, and the ancillary ligands. [on SciFinder(R)]",
         "issn" : "0020-1669",
         
         "doi" : "10.1021/acs.inorgchem.5b02541",
         
         "bibtexKey": "Mandal.2016"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/285037b5699fc4d95fb243b6f4e00bb97/b_schwederski",         
         "tags" : [
            "azodicarbonyl","complex","complex;electron","complex;mixed","complex;substituent","configuration","dinuclear","effect","electrochem","ruthenium","valence"
         ],
         
         "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",
         "user" : "b_schwederski",
         "description" : "",
         "date" : "2019-07-15 13:41:23",
         "changeDate" : "2019-07-15 11:42:10",
         "count" : 3,
         "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"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/2ffc8ac9ac6e5c7681f8e0ed77243b8c9/b_schwederski",         
         "tags" : [
            "ESR","carbonyl","complex","complex;crystal","complex;mol","complex;ruthenium","conjugated","conjugation","effect","electrooxidn;spectroelectrochem","hexenyl","oxidn","phosphine","pi","potential","prepn","pyrenylethenyl","pyridine","ruthenium","spectra","structure","styryl","vinyl","vinylruthenium"
         ],
         
         "intraHash" : "ffc8ac9ac6e5c7681f8e0ed77243b8c9",
         "interHash" : "9784e4c65bc618f661506a3660a9a016",
         "label" : "Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A case of non-innocence in organometallic chemistry",
         "user" : "b_schwederski",
         "description" : "",
         "date" : "2019-07-15 13:41:23",
         "changeDate" : "2019-07-15 11:42:10",
         "count" : 3,
         "pub-type": "article",
         "journal": "Journal of the American Chemical Society",
         "year": "2008", 
         "url": "", 
         
         "author": [ 
            "Joerg Maurer","Michael Linseis","Biprajit Sarkar","Brigitte Schwederski","Mark Niemeyer","Wolfgang Kaim","Stanislav Zalis","Chris Anson","Manfred Zabel","Rainer F. Winter"
         ],
         "authors": [
         	
            	{"first" : "Joerg",	"last" : "Maurer"},
            	{"first" : "Michael",	"last" : "Linseis"},
            	{"first" : "Biprajit",	"last" : "Sarkar"},
            	{"first" : "Brigitte",	"last" : "Schwederski"},
            	{"first" : "Mark",	"last" : "Niemeyer"},
            	{"first" : "Wolfgang",	"last" : "Kaim"},
            	{"first" : "Stanislav",	"last" : "Zalis"},
            	{"first" : "Chris",	"last" : "Anson"},
            	{"first" : "Manfred",	"last" : "Zabel"},
            	{"first" : "Rainer F.",	"last" : "Winter"}
         ],
         "volume": "130","number": "1","pages": "259--268","abstract": "A series of vinylruthenium bis-phosphine five- and six-coordinated complexes with non-conjugated 1-hexenyl, conjugated styryl and pyrenylethenyl ligands were prepd.; the effects of conjugation of the arom. system with vinyl p-bond on oxidn. potential, stability of the oxidated species, ESR spectra and IR CO-stretching bands were systematically explored by IR-spectroelectrochem. and DFT calcns.  Hydrometalation of 1-hexyne, phenylacetylene and 1-ethynylpyrene affords the corresponding five-coordinated ruthenium complexes [(PR3)2Cl(CO)RuCH:CHR1] (1a-3a; R = Ph, R1 = Bu, Ph, 1-pyrenyl; 1c-3c; R = iPr, same R1) and their octahedral pyridine adducts [(PPh3)2Cl(CO)(4-EtO2CC5H4N-kN)RuCH:CHR1] (1b-3b; same R1).  Crystal structures of 1b, 1c, 3c and 3a·PPh3 and enynyl complex [Ru(CO)Cl(PPh3)2(h1:h2-nBuHC:CHC$\\equiv$CnBu)], the result of coupling of the hexenyl ligand of complex 1a with another mol. of 1-hexyne, are reported.  All vinyl complexes undergo a one-electron oxidn. at fairly low potentials and a second oxidn. at more pos. potentials.  Anodic half-wave or peak potentials show a progressive shift to lower values as p-conjugation within the vinyl ligand increases.  Carbonyl band shifts of the metal-bonded CO ligand upon monooxidn. are significantly smaller than is expected of a metal-centered oxidn. process and are further diminished as the vinyl CH:CH entity is incorporated into a more extended p-system.  ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the av. g-value from that of the free electron.  The vinyl ligands thus strongly contribute to or even dominate the anodic oxidn. processes.  This renders them a class of truly \\dqnon-innocent\\dq ligands in organometallic ruthenium chem.  Exptl. findings are fully supported by quantum chem. calcns.  The contribution of the vinyl ligand to the HOMO increases from 46\\% (Ru-vinyl delocalized) to 84\\% (vinyl dominated) as R changes from Bu to 1-pyrenyl. [on SciFinder(R)]",
         "issn" : "0002-7863",
         
         "doi" : "10.1021/ja075547t",
         
         "bibtexKey": "Maurer.2008"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/282951d10265eecfa5b6b21bfda53531e/b_schwederski",         
         "tags" : [
            "axial","complex","effect","effect;spectroelectrochem","electrochem","ligand","ligation","nitrosyl","porphyrin","reaction","redox","ruthenium","study","tetraphenylporphyrin"
         ],
         
         "intraHash" : "82951d10265eecfa5b6b21bfda53531e",
         "interHash" : "8b4d411242b7805179b426464fa2163c",
         "label" : "Redox Properties of Ruthenium Nitrosyl Porphyrin Complexes with Different Axial Ligation: Structural, Spectroelectrochemical (IR, UV-Visible, and EPR), and Theoretical Studies",
         "user" : "b_schwederski",
         "description" : "",
         "date" : "2019-07-15 13:41:23",
         "changeDate" : "2019-07-15 11:42:10",
         "count" : 3,
         "pub-type": "article",
         "journal": "Inorganic Chemistry",
         "year": "2008", 
         "url": "", 
         
         "author": [ 
            "Priti Singh","Atanu Kumar Das","Biprajit Sarkar","Mark Niemeyer","Federico Roncaroli","Jose A. Olabe","Jan Fiedler","Stanislav Zalis","Wolfgang. Kaim"
         ],
         "authors": [
         	
            	{"first" : "Priti",	"last" : "Singh"},
            	{"first" : "Atanu Kumar",	"last" : "Das"},
            	{"first" : "Biprajit",	"last" : "Sarkar"},
            	{"first" : "Mark",	"last" : "Niemeyer"},
            	{"first" : "Federico",	"last" : "Roncaroli"},
            	{"first" : "Jose A.",	"last" : "Olabe"},
            	{"first" : "Jan",	"last" : "Fiedler"},
            	{"first" : "Stanislav",	"last" : "Zalis"},
            	{"first" : "Wolfgang.",	"last" : "Kaim"}
         ],
         "volume": "47","number": "16","pages": "7106--7113","abstract": "Exptl. and computational results for different Ru nitrosyl porphyrin complexes [(Por)Ru(NO)(X)]n+ (Por2- = tetraphenylporphyrin dianion (TPP2-) or octaethylporphyrin dianion (OEP2-) and X = H2O (n = 1, 2, 3) or pyridine, 4-cyanopyridine, or 4-N,N-dimethylaminopyridine (n = 1, 0)) are reported with respect to their electron-transfer behavior.  The structure of [(TPP)Ru(NO)(H2O)]BF4 is established as an MNO species with an almost-linear RuNO arrangement at 178.1(3)°.  [(Por)Ru(NO)(H2O)]BF4 undergoes 2 reversible 1-electron oxidn. processes.  Spectroelectrochem. measurements (IR, UV-visible-NIR, and EPR) indicate that the 1st oxidn. occurs on the porphyrin ring, as evident from the appearance of diagnostic porphyrin radical-anion vibrational bands (1530 cm-1 for OEP.bul.- and 1290 cm-1 for TPP.bul.-), from the small shift of $\\sim$20 cm-1 for nNO and from the EPR signal at giso $\\approx$ 2.00.  The 2nd oxidn., which is electrochem. reversible for the OEP compd., shows a 55. cm-1 shift in nNO, suggesting a partially metal-centered process.  [(Por)Ru(NO)(X)]BF4, where X = pyridines, undergo a reversible 1-electron redn.  The site of the redn. was detd. by spectroelectrochem. studies to be NO-centered with a ca. -300 cm-1 shift in nNO.  The EPR response of the NO.bul. complexes was essentially unaffected by the variation in the substituted pyridines X.  DFT calcns. support the interpretation of the exptl. results because the HOMO of [(TPP)Ru(NO)(X)]+, where X = H2O or pyridines, is centered at the porphyrin p system, whereas the LUMO of [(TPP)Ru(NO)(X)]+ has $\\sim$50\\% p*(NO) character.  This confirms that the (1st) oxidn. of [(Por)Ru(NO)(H2O)]+ occurs on the porphyrin ring whereas the redn. of [(Por)Ru(NO)(X)]+ is largely NO-centered with the metal remaining in the low-spin Ru(II) state throughout.  The 4\\% pyridine contribution to the LUMO of [(TPP)Ru(NO)(py)]+ is correlated with the stability of the reduced form as opposed to that of the aqua complex. [on SciFinder(R)]",
         "issn" : "0020-1669",
         
         "doi" : "10.1021/ic702371t",
         
         "bibtexKey": "Singh.2008b"

      }
,
      {
         "type" : "Publication",
         "id"   : "https://puma.ub.uni-stuttgart.de/bibtex/2749b81ca5cbb600a1eaf5a100b0e9d5f/b_schwederski",         
         "tags" : [
            "alkylation","calcn","complex","complex;spectroelectrochem","crystal","dipivaloylhydrazido","effect","mol","osmium","prepn","protonation","ruthenium","structure","structure;electron","transfer"
         ],
         
         "intraHash" : "749b81ca5cbb600a1eaf5a100b0e9d5f",
         "interHash" : "9408374c2f25345678ce79d71fdf8514",
         "label" : "Metalloradical Compounds with 1,2-Dipivaloylhydrazido Ligands: Electron Transfer and Alkylation/Protonation Effects",
         "user" : "b_schwederski",
         "description" : "",
         "date" : "2019-07-15 13:41:23",
         "changeDate" : "2019-07-15 11:42:10",
         "count" : 3,
         "pub-type": "article",
         "journal": "European Journal of Inorganic Chemistry",
         "year": "2019", 
         "url": "", 
         
         "author": [ 
            "Sudipta Mondal","Vasileios Filippou","Martina Bubrin","Brigitte Schwederski","Jan Fiedler","Wolfgang. Kaim"
         ],
         "authors": [
         	
            	{"first" : "Sudipta",	"last" : "Mondal"},
            	{"first" : "Vasileios",	"last" : "Filippou"},
            	{"first" : "Martina",	"last" : "Bubrin"},
            	{"first" : "Brigitte",	"last" : "Schwederski"},
            	{"first" : "Jan",	"last" : "Fiedler"},
            	{"first" : "Wolfgang.",	"last" : "Kaim"}
         ],
         "volume": "2019","number": "21","pages": "2639--2647","abstract": "Under oxidative conditions the complexes M(bpy)2Cl2, M = Ru or Os, react with 1,2-dipivaloylhydrazine H2L = tBuC(O)-NH-NH-C(O)-tBu to yield the paramagnetic compds. [M(L)(bpy)2](PF6) 1(PF6), M = Ru and 2(PF6), M = Os.  Crystal structures of 1(ClO4) and 2(PF6) reveal an NNCO chelate coordination of L with d(NN) $\\approx$ 1.39 \\AA.  EPR spectroscopy suggests a metal/ligand mixed situation for the unpaired electron, with 29 \\% (Ru, 1+) or 46 \\% (Os, 2+) metal spin contribution according to DFT calcns.  Both complex cations exhibit reversible one-electron oxidn. and redn. (Kc $\\approx$ 1019 for 1+ and 1012 for 2+) which could also be monitored by IR (nCO) and UV/Vis-NIR spectroelectrochem.  These data confirm a metal/ligand orbital mixing MII(L·-) $łeftrightarrow$ MIII(L2-), with the osmium analog favoring the latter alternative.  Reaction of Ru(bpy)2Cl2 under non-oxidizing conditions yields the intermediate (1H)(PF6) which could be oxidatively deprotonated to 1+ or methylated to (1Me)(PF6), both identified by 1H and 13C NMR.  While oxidn. of (1H)+ proceeds irreversibly due to proton loss, the reversible spectroelectrochem. oxidn. of (1Me)+ suggests a metal-based process RuII(LMe-) $\\rightarrow$ RuIII(LMe-).  The results reveal that not only dinuclear complexes of 1,2-diacylhydrazido ligands but also mononuclear analogs are distinguished by remarkably variable metal/ligand mixed contributions to the frontier orbitals. [on SciFinder(R)]",
         "issn" : "1434-1948",
         
         "doi" : "10.1002/ejic.201900391",
         
         "bibtexKey": "Mondal.2019"

      }
	  
   ]
}