{ "types" : { "Bookmark" : { "pluralLabel" : "Bookmarks" }, "Publication" : { "pluralLabel" : "Publications" }, "GoldStandardPublication" : { "pluralLabel" : "GoldStandardPublications" }, "GoldStandardBookmark" : { "pluralLabel" : "GoldStandardBookmarks" }, "Tag" : { "pluralLabel" : "Tags" }, "User" : { "pluralLabel" : "Users" }, "Group" : { "pluralLabel" : "Groups" }, "Sphere" : { "pluralLabel" : "Spheres" } }, "properties" : { "count" : { "valueType" : "number" }, "date" : { "valueType" : "date" }, "changeDate" : { "valueType" : "date" }, "url" : { "valueType" : "url" }, "id" : { "valueType" : "url" }, "tags" : { "valueType" : "item" }, "user" : { "valueType" : "item" } }, "items" : [ { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/27ee3f089225f37c969230bdbd913a5ac/huebleriac", "tags" : [ "DFT","calcn","complex","complex;dinuclear","crystal","dinuclear","electrochem","indigodiphenylimine","pentanedionato","prepn","ruthenium","structure" ], "intraHash" : "7ee3f089225f37c969230bdbd913a5ac", "interHash" : "72f3833a886261819859be6fcfeb908e", "label" : "A Diruthenium Complex of a \\dqNindigo\\dq Ligand", "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": "2013", "url": "", "author": [ "Prasenjit Mondal","Fabian Ehret","Martina Bubrin","Amit Das","Shaikh M. Mobin","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Prasenjit", "last" : "Mondal"}, {"first" : "Fabian", "last" : "Ehret"}, {"first" : "Martina", "last" : "Bubrin"}, {"first" : "Amit", "last" : "Das"}, {"first" : "Shaikh M.", "last" : "Mobin"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "52","number": "15","pages": "8467--8475","abstract": "(μ-Nindigo)[Ru(acac)2]2 (1), H2(Nindigo) = indigo-N,N'-diphenylimine and acac- = 2,4-pentanedionate, was structurally characterized in the rac form, which exhibits two edge-sharing six-membered chelate rings involving ruthenium, and the former b-diketiminato functions with a twist angle of 33.9° around the central C-C bond. The metric parameters suggest a neutral p acceptor bridge contg. coupled s-trans configurated a-diimines, which are coordinated by two ruthenium(II) centers. DFT calcns. confirm the exptl. structure and oxidn. state assignment of the rac form; both diastereoisomers are present in soln. according to 1H NMR spectroscopy. A very intense long-wavelength MLCT absorption at 630 nm (e = 66,800 M-1 cm-1) and a weaker near-IR band at 1120 nm (e = 3000 M-1 cm-1) are obsd. for the CH3CN soln. Reversible 1-electron redn. and oxidn. steps were studied by cyclic voltammetry, differential pulse voltammetry, EPR, and UV-visible-NIR spectroelectrochem. to exhibit metal-centered oxidn. and mixed metal/ligand-centered redn. These results are supported by TD-DFT calcns. of the species rac- or meso-1n, n = 3+, 2+, +, 0, -, 2-. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic400390b", "bibtexKey": "Mondal.2013" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/28bda747c0cfbaafe0582064ce54f7efb/huebleriac", "tags" : [ "DFT","bridged","complex","complex;vinylpyridine","delocalization","electrochem","electron","phenylenevinylene","prepn","ruthenium","spectroelectrochem","tetranuclear","vinylpyridine" ], "intraHash" : "8bda747c0cfbaafe0582064ce54f7efb", "interHash" : "fe455fd1612db6efc82c725ad2ab8b9e", "label" : "Towards new organometallic wires: Tetraruthenium complexes bridged by phenylenevinylene and vinylpyridine ligands", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Chemistry - A European Journal", "year": "2007", "url": "", "author": [ "Joerg Maurer","Biprajit Sarkar","Wolfgang Kaim","Rainer F. Winter","Stanislav. Zalis" ], "authors": [ {"first" : "Joerg", "last" : "Maurer"}, {"first" : "Biprajit", "last" : "Sarkar"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Rainer F.", "last" : "Winter"}, {"first" : "Stanislav.", "last" : "Zalis"} ], "volume": "13","number": "36","pages": "10257--10272","abstract": "Tetranuclear [(PiPr3)2(CO)ClRu(μ-CH:CHpy)RuCl(CO)(PPh3)22(m-CH:CHC6H4CH:CH-1,4)] (3a; py = pyridin-4-yl) and [(PiPr3)2(CO)ClRu(μ-CH:CHpy)RuCl(CO)(PPh3)22(m-CH:CHC6H4CH:CH-1,3)] (3b), which contain vinylpyridine ligands that connect peripheral Ru(PiPr3)2(CO)Cl units to a central divinylphenylene-bridged diruthenium core, were prepd. and studied. These complexes, in various oxidn. states up to the tetracation level, were characterized by std. electrochem. and spectroelectrochem. techniques, including IR, UV/visible/NIR and ESR spectroscopy. A comparison with the results for the vinylpyridine-bridged dinuclear complex [(PiPr3)2(CO)ClRu(m-CH:CHpy)RuCl(CO)(PPh3)2(CH:CHPh)] (6) and the divinylphenylene-bridged complexes [(EtOOCpy)(CO)Cl(PPh3)2Ru2(m-CH:CHC6H4CH:CH-1,4)] (8a) and [(EtOOCpy)(CO)Cl(PPh3)2Ru2(m-CH:CHC6H4CH:CH-1,3)] (8b), which represent the outer sections (6) or the inner core (8a,b) of complexes 3a,b, and with mononuclear [(EtOOCpy)(CO)(PPh3)2RuCl(CH:CHPh)] (7) indicate that every accessible oxidn. process is primarily centered on one of the vinyl ligands, with smaller contributions from the metal centers. The exptl. results and quantum chem. calcns. indicate charge- and spin-delocalization across the central divinylphenylenediruthenium part of 3a,b or the styrylruthenium unit of 6, but not beyond. The energy gap between the higher lying styryl- or divinylphenylenediruthenium-based and the lower occupied vinylpyridineruthenium-based orbitals increases in the order 6 \\textless 3b \\textless 3a and thus follows the conjugation within the non-heteroatom-substituted arom. vinyl ligand. [on SciFinder(R)]", "issn" : "0947-6539", "doi" : "10.1002/chem.200700459", "bibtexKey": "Maurer.2007" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2495b62852b43f3c10fe39672eabbbb1a/huebleriac", "tags" : [ "DFT","Raman","catalysis","cobalt","complex;EPR","cyclopentadienyl","diimine","excited","hydride","intermediate","iridium;reduced","resonance","rhodium","spectra","state","transfer" ], "intraHash" : "495b62852b43f3c10fe39672eabbbb1a", "interHash" : "6f51281eab0ac1f7618262037b772809", "label" : "Reduced and excited states of the intermediates (a-diimine)(C5R5)Rh in hydride transfer catalysis schemes: EPR and resonance Raman spectroscopy, and comparative DFT calculations of Co, Rh and Ir analogues", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Dalton Transactions", "year": "2004", "url": "", "author": [ "Monika Sieger","Wolfgang Kaim","Derk J. Stufkens","Theo L. Snoeck","Hermann Stoll","Stanislav. Zalis" ], "authors": [ {"first" : "Monika", "last" : "Sieger"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Derk J.", "last" : "Stufkens"}, {"first" : "Theo L.", "last" : "Snoeck"}, {"first" : "Hermann", "last" : "Stoll"}, {"first" : "Stanislav.", "last" : "Zalis"} ], "number": "22","pages": "3815--3821","abstract": "The electronic structures of the highly air-sensitive intermediates (N-N)(C5Me5)Rh, (N-N = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym), 2,2'-bipyrazine (bpz) and 3,3'-bipyridazine (bpdz)) of hydride transfer catalysis schemes were studied through resonance Raman (rR) spectroscopy and through EPR of the reduced forms [(N-N)(C5Me5)Rh].bul.-. The rR results are compatible with a predominant MLCT character of the lowest excited states [(N-N)(C5Me5)Rh]*, and the EPR spectra of the reduced states reveal the presence of anion radical ligands, (N-N).bul.-, coordinated by unusually electron rich rhodium(I) centers. The exptl. results, including the assignments of electronic transitions, are supported by DFT calcns. for the model compds. [(N-N)(C5H5)Rh]o/.bul.-, N-N = bpy or bpym. The calcns. confirm a significant but not complete mixing of metal and ligand orbitals in the LUMO which still retains about 3/4 p*(N-N) character. DFT calcns. on (bpy)(C5H5)M and [(bpy)(C5H5)ClM]+, M = Co, Rh, Ir, agree with the exptl. results such as the differences between the homologues, esp. the different LUMO characters of the precursor cations in the case of Co ($\\rightarrow$dM) and Rh or Ir ($\\rightarrow$p*(bpy)). [on SciFinder(R)]", "issn" : "1477-9226", "doi" : "10.1039/B411892H", "bibtexKey": "Sieger.2004" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/23c752202409e7e5e56d0f89b0d435677/huebleriac", "tags" : [ "DFT","accepting","complex;spectroelectrochem","electron","iron","nitrogen","nitrosyl","oxide","porphyrin","redn","redox","sibling","spin","state" ], "intraHash" : "3c752202409e7e5e56d0f89b0d435677", "interHash" : "c7dea2fc23ec5b33caf39cd817b22ac1", "label" : "Spectroelectrochemical Evidence for the Nitrosyl Redox Siblings NO+, NO., and NO- Coordinated to a Strongly Electron-Accepting FeII Porphyrin: DFT Calculations Suggest the Presence of High-Spin States after Reduction of the FeII-NO- Complex", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Chemistry - A European Journal", "year": "2011", "url": "", "author": [ "Juan Pellegrino","Ralph Huebner","Fabio Doctorovich","Wolfgang. Kaim" ], "authors": [ {"first" : "Juan", "last" : "Pellegrino"}, {"first" : "Ralph", "last" : "Huebner"}, {"first" : "Fabio", "last" : "Doctorovich"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "17","number": "28","pages": "7868-7874, S7868/1-S7868/9","abstract": "Exptl. and computational results for the electron-deficient porphyrin complex [Fe(NO)(TFPPBr8)] (1; TFPPBr8 = 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin) are reported with respect to its electron-transfer behavior. Complex 1 undergoes three 1-electron processes: two reversible redns. and one irreversible oxidn. Spectroelectrochem. measurements (IR and UV/visible/NIR spectroscopy) of 14NO- and 15NO-contg. material indicate that the 1st redn. to 1- occurs largely on the NO ligand to produce nitroxyl anion (NO-) character, as evident from the considerable change in nNO from 1715 to around 1550 cm-1. The 2nd redn. to 12- does not result in a further shift of nNO to lower frequencies, but to a surprising high-energy shift to 1590 cm-1. This and the notable changes of the characteristic porphyrin vibrations as well as significant changes of the UV/visible absorptions indicate a porphyrin-centered process; DFT calcns. predict the shift of nNO to higher frequencies for the intermediate- and high-spin states of 12-. The oxidn. of 1 is irreversible on the voltammetry timescale, but chem. reversible in spectroelectrochem. expts., suggesting that the cationic form dissocs. to the corresponding ferric porphyrin and NO. DFT calcns. support the interpretation of the exptl. results. [on SciFinder(R)]", "issn" : "0947-6539", "doi" : "10.1002/chem.201003516", "bibtexKey": "Pellegrino.2011b" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/239036ee1d295804f02c0c2b6088dc189/huebleriac", "tags" : [ "DFT","chloro","complex","complex;nitrosyl","electrochem","iridium","nitrosyl","oxidn","redn","ruthenium","state" ], "intraHash" : "39036ee1d295804f02c0c2b6088dc189", "interHash" : "3f220d59d8af9082a347674682a30cd5", "label" : "Establishing the NO oxidation state in complexes [Cl5(NO)M]n-, M = Ru or Ir, through experiments and DFT calculations", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Dalton Transactions", "year": "2004", "url": "", "author": [ "Monika Sieger","Biprajit Sarkar","Stanislav Zalis","Jan Fiedler","Natalia Escola","Fabio Doctorovich","Jose A. Olabe","Wolfgang. Kaim" ], "authors": [ {"first" : "Monika", "last" : "Sieger"}, {"first" : "Biprajit", "last" : "Sarkar"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Natalia", "last" : "Escola"}, {"first" : "Fabio", "last" : "Doctorovich"}, {"first" : "Jose A.", "last" : "Olabe"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "number": "12","pages": "1797--1800","abstract": "Predominantly NO-centered redn. was obsd. by EPR and IR spectroelectrochem. to occur reversibly at low temps. for [Cl5Ir(NO)]-. But the [Cl5Ru(NO)]2- ion was found to undergo only irreversible redn. but reversible oxidn. to a Ru(iii) species at -40°. DFT calcns. were used to establish the electronic structures and to rationalize the different stabilities. The calcns. also reveal orientation-dependent energies and EPR properties between staggered and eclipsed conformations. [on SciFinder(R)]", "issn" : "1477-9226", "doi" : "10.1039/B404121F", "bibtexKey": "Sieger.2004b" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2c01231f2d341e664fb99950dbe713533/huebleriac", "tags" : [ "DFT","bipyridine","complex","crystal","electrochem","ellagate","pentanedionate","phenylazopyridine","phenylazopyridine;ruthenium","prepn","ruthenium","structure" ], "intraHash" : "c01231f2d341e664fb99950dbe713533", "interHash" : "e4385ecd5267f5d041a931741126571e", "label" : "Noninnocently Behaving Bridging Anions of the Widely Distributed Antioxidant Ellagic Acid in Diruthenium Complexes", "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": "2015", "url": "", "author": [ "Abhishek Mandal","Anita Grupp","Brigitte Schwederski","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Abhishek", "last" : "Mandal"}, {"first" : "Anita", "last" : "Grupp"}, {"first" : "Brigitte", "last" : "Schwederski"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "54","number": "20","pages": "10049--10057","abstract": "Dinuclear compds. [L2Ru(m-E)RuL2]n where L is acetylacetonate (acac-, 2,4-pentanedionate), 2,2'-bipyridine (bpy), or 2-phenylazopyridine (pap) and EH4 is ellagic acid, an antioxidative bis-catechol natural product, were studied by voltammetric and spectroelectrochem. techniques (UV-vis-NIR and ESR). The electronic structures of the isolated forms (NBu4)2[(acac)2Ru(m-E)Ru(acac)2] ((NBu4)2[1]), [(bpy)2Ru(m-E)Ru(bpy)2]ClO4 ([2]ClO4), and [(pap)2Ru(m-E)Ru(pap)2] ([3]) were characterized by d. functional theory (DFT) in conjunction with EPR and UV-vis-NIR measurements. The crystal structure of (NBu4)2[1] revealed the meso form and a largely planar Ru(m-E)Ru center. Several addnl. charge states of the compds. were electrochem. accessible and were identified mostly as complexes with noninnocently behaving pap0/.bul.- or bridging ellagate (En-) anions (n = 2, 3, 4) but not as mixed-valence intermediates. The free anions En-, n = 1-4, were calcd. by time-dependent DFT to reveal NIR transitions for the radical forms with n = 1 and 3 and a triplet ground state for the bis(o-semiquinone) dianion E2-. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/acs.inorgchem.5b01868", "bibtexKey": "Mandal.2015c" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2c2d9f8d10c4e91bd2ae47cd61dba3dff/huebleriac", "tags" : [ "DFT","EPR","cyclopentadienyl","dicarbonyl","electrochem","electron","geometry","iron","redox","structure","tetracyanoethene","tetracyanoquinodimethane","transfer","transfer;Moessbauer","transfer;electronic","transfer;optimized" ], "intraHash" : "c2d9f8d10c4e91bd2ae47cd61dba3dff", "interHash" : "0d6d985f3a7d15cf424c24b7e9f26385", "label" : "Tetranuclear Complexes of [Fe(CO)2(C5H5)]+ with TCNX Ligands (TCNX = TCNE, TCNQ, TCNB): Intramolecular Electron Transfer Alternatives in Compounds (m4-TCNX)[MLn]4", "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": "2007", "url": "", "author": [ "Amarendra N. Maity","Brigitte Schwederski","Biprajit Sarkar","Stanislav Zalis","Jan Fiedler","Sanjib Kar","Goutam K. Lahiri","Carole Duboc","Matthias Grunert","Philipp Guetlich","Wolfgang. Kaim" ], "authors": [ {"first" : "Amarendra N.", "last" : "Maity"}, {"first" : "Brigitte", "last" : "Schwederski"}, {"first" : "Biprajit", "last" : "Sarkar"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Sanjib", "last" : "Kar"}, {"first" : "Goutam K.", "last" : "Lahiri"}, {"first" : "Carole", "last" : "Duboc"}, {"first" : "Matthias", "last" : "Grunert"}, {"first" : "Philipp", "last" : "Guetlich"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "46","number": "18","pages": "7312--7320","abstract": "(μ4-TCNX)[Fe(CO)2(C5H5)]4(BF4)4 were prepd. as light-sensitive materials from [Fe(CO)2(C5H5)(THF)](BF4) and the corresponding TCNX ligands (TCNE = tetracyanoethene, TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, TCNB = 1,2,4,5-tetracyanobenzene). Whereas the TCNE and TCNQ complexes are extremely easily reduced species with redn. potentials \\textgreater+0.3 V vs. ferrocenium/ferrocene, the tetranuclear complex of TCNB exhibits a significantly more neg. redn. potential at $\\sim$-1.0 V. Even for the complexes with strongly p-accepting TCNE and TCNQ, the very pos. redn. potentials, the unusually high nitrile stretching frequencies \\textgreater2235 cm-1, and the high-energy charge-transfer transitions indicate negligible metal-to-ligand electron transfer in the ground state, corresponding to a largely unperturbed (TCNX°)(FeII)4 formulation of oxidn. states as caused by orthogonality between the metal-centered HOMO and the p* LUMO of TCNX. Mossbauer spectroscopy confirms the low-spin Fe(II) state, and DFT calcns. suggest coplanar TCNE and TCNQ bridging ligands in the complex tetracations. One-electron redn. to the 3+ forms of the TCNE and TCNQ complexes produces EPR spectra which confirm the predominant ligand character of the then singly occupied MO through isotropic g values slightly \\textless2, in addn. to a negligible g anisotropy of frozen solns. at frequencies up to 285 GHz and also through an unusually well-resolved soln. X band EPR spectrum of (μ4-TCNE)[Fe(CO)2(C5H5)]43+ which shows four equiv. [Fe(CO)2(C5H5)]+ moieties through 57Fe and 13C(CO) hyperfine coupling in nonenriched material. DFT calcns. reproduce the exptl. EPR data. A survey of discrete TCNE and TCNQ complexes [(m4-TCNX)(MLn)4] exhibits a dichotomy between the systems (μ4-TCNX)[Fe(CO)2(C5H5)]44+ and (μ4-TCNQ)[Re(CO)3(bpy)]44+ with their negligible metal-to-ligand electron transfer and several other compds. of TCNE or TCNQ with Mn, Ru, Os, or Cu complex fragments which display evidence for a strong such interaction, i.e., an appreciable value d in the formulation (μ4-TCNXδ-)[Mx+δ/4Ln]4. Irreversibility of the 1st redn. of (μ4-TCNB)[Fe(CO)2(C5H5)]4(BF4)4 precluded spectroelectrochem. studies; however, the high-energy CN stretching frequencies and charge transfer absorptions of that TCNB analog also confirm the exceptional position of (μ4-TCNX)[Fe(CO)2(C5H5)]4(BF4)4. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic062253k", "bibtexKey": "Maity.2007" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2727254f323a53ae10a95ea3109f3d8b0/huebleriac", "tags" : [ "DFT","aqua","benzoquinonediimine","calcn","catalyst","catalyst;ruthenium","chloro","complex","complex;olefin","crystal","electrochem","epoxidn","methanetrispyrazole","prepn","ruthenium","structure" ], "intraHash" : "727254f323a53ae10a95ea3109f3d8b0", "interHash" : "0985d2e9d0f121c64939bce49921d0f9", "label" : "Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimine", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Dalton Transactions", "year": "2013", "url": "", "author": [ "Hemlata Agarwala","Fabian Ehret","Abhishek Dutta Chowdhury","Somnath Maji","Shaikh M. Mobin","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Hemlata", "last" : "Agarwala"}, {"first" : "Fabian", "last" : "Ehret"}, {"first" : "Abhishek Dutta", "last" : "Chowdhury"}, {"first" : "Somnath", "last" : "Maji"}, {"first" : "Shaikh M.", "last" : "Mobin"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "42","number": "10","pages": "3721--3734","abstract": "Diamagnetic [Ru(tpm)(bqdi)(Cl)]ClO4 ([1]ClO4) (tpm = tris(1-pyrazolyl)methane, bqdi = o-benzoquinonediimine) and [Ru(tpm)(bqdi)(H2O)](ClO4)2 ([2](ClO4)2) were synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) \\AA in [1]ClO4; 1.316(7)/1.314(7) \\AA in mol. A and 1.315(6)/1.299(7) \\AA in mol. B of [2](ClO4)2] imply its fully oxidized quinonediimine (bqdi0) character. DFT calcns. of 1+ confirm the RuII-bqdi0 vs. the antiferromagnetically coupled RuIII-bqdi√- alternative. The 1H NMR spectra of [1]ClO4 in different solvents show variations in chem. shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH3CN/0.1 mol dm-3 Et4NClO4, [1]ClO4 undergoes one reversible RuII .dblharw. RuIII oxidn. and two redns., the reversible first electron uptake being bqdi based (bqdi0/bqdi$\\surd$-). The electrogenerated paramagnetic RuIII-bqdi0 (12+) and RuII-Q√- (1) exhibit RuIII-type (12+: \\textlessg\\textgreater = 2.211/Dg = 0.580) and radical-type (1: g = 1.988) EPR signals, resp., as is confirmed by calcd. spin densities (Ru: 0.767 in 12+, bqdi: 0.857 in 1). The aqua complex [2](ClO4)2 exhibits two 1-electron oxidns. at pH = 7, suggesting the formation of RuIV:O species. The electronic spectral features of 1n (n = charge assocd. with the different redox states of the chloro complex: 2+, 1+, 0) in CH3CN and of 22+ in H2O were interpreted based on the TD-DFT calcns. The application potential of the aqua complex 22+ as a pre-catalyst towards the epoxidn. of olefins was explored in the presence of the sacrificial oxidant PhI(OAc)2 in CH2Cl2 at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calcns. based on styrene as the model substrate predict that the epoxidn. reaction proceeds through a concerted transition state pathway. [on SciFinder(R)]", "issn" : "1477-9226", "doi" : "10.1039/c2dt32402d", "bibtexKey": "Agarwala.2013" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2407a9f92187861fb201adf6a13b4a935/huebleriac", "tags" : [ "DFT","EPR","acetylacetonato","bisphenyliminoacenaphthene","calcn","complex","complex;ruthenium","crystal","electrochem","prepn","ruthenium","structure","tetrakispyridylpyrazine" ], "intraHash" : "407a9f92187861fb201adf6a13b4a935", "interHash" : "cb3fb851b57939848e82c034871e6472", "label" : "Sensitivity of a Strained C-C Single Bond to Charge Transfer: Redox Activity in Mononuclear and Dinuclear Ruthenium Complexes of Bis(arylimino)acenaphthene (BIAN) Ligands", "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": "2014", "url": "", "author": [ "Prasenjit Mondal","Hemlata Agarwala","Rahul Dev Jana","Sebastian Plebst","Anita Grupp","Fabian Ehret","Shaikh M. Mobin","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Prasenjit", "last" : "Mondal"}, {"first" : "Hemlata", "last" : "Agarwala"}, {"first" : "Rahul Dev", "last" : "Jana"}, {"first" : "Sebastian", "last" : "Plebst"}, {"first" : "Anita", "last" : "Grupp"}, {"first" : "Fabian", "last" : "Ehret"}, {"first" : "Shaikh M.", "last" : "Mobin"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "53","number": "14","pages": "7389--7403","abstract": "[Ru(acac)2(BIAN)], BIAN = bis(arylimino)acenaphthene (aryl = Ph (1a), 4-MeC6H4 (2a), 4-OMeC6H4 (3a), 4-ClC6H4 (4a), 4-NO2C6H4 (5a)), were synthesized and structurally, electrochem., spectroscopically, and computationally characterized. The a-diimine sections of the compds. exhibit intrachelate ring bond lengths 1.304 \\AA \\textless d(CN) \\textless 1.334 and 1.425 \\AA \\textless d(CC) \\textless 1.449 \\AA, which indicate considerable metal-to-ligand charge transfer in the ground state, approaching a RuIII(BIAN.bul.-) oxidn. state formulation. The particular structural sensitivity of the strained peri-connecting C-C bond in the BIAN ligands toward metal-to-ligand charge transfer is discussed. Oxidn. of [Ru(acac)2(BIAN)] produces EPR and UV-visible-NIR (NIR = near IR) spectroelectrochem. detectable RuIII species, while the redn. yields predominantly BIAN-based spin, in agreement with d. functional theory (DFT) spin-d. calcns. Variation of the substituents from CH3 to NO2 has little effect on the spin distribution but affects the absorption spectra. Dinuclear (μ-tppz)[Ru(Cl)(BIAN)]2(ClO4)2, tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; aryl (BIAN) = Ph ([1b](ClO4)2), 4-MeC6H4 ([2b](ClO4)2), 4-OMeC6H4 ([3b](ClO4)2), 4-ClC6H4 ([4b](ClO4)2), were also obtained and investigated. The structure detn. of [2b](ClO4)2 and [3b](ClO4)2 reveals trans configuration of the chloride ligands and unreduced BIAN ligands. The DFT and spectroelectrochem. results (UV-visible-NIR, EPR) indicate oxidn. to a weakly coupled RuIIIRuII mixed-valent species but redn. to a tppz-centered radical state. The effect of the p electron-accepting BIAN ancillary ligands is to diminish the metal-metal interaction due to competition with the acceptor bridge tppz. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic500730m", "bibtexKey": "Mondal.2014d" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2f76a12cb2c5493fd61d84ae2557d2ac2/huebleriac", "tags" : [ "DFT","bipyridine","complex","crystal","electrochem","electron","iminobenzoquinone","one","osmium","oxidn","prepn;paramagnetic","redn","redox;spectroelectrochem","state","structure" ], "intraHash" : "f76a12cb2c5493fd61d84ae2557d2ac2", "interHash" : "ab658bd7a6a945178cda107a61eb64c9", "label" : "The intricate paramagnetic state of [Os(Q)2(bpy)]+, Q = 4,6-di-tert-butyl-o-iminobenzoquinone", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Dalton Transactions", "year": "2012", "url": "", "author": [ "Dipanwita Das","Thomas Michael Scherer","Amit Das","Tapan Kumar Mondal","Shaikh M. Mobin","Jan Fiedler","Jose Luis Priego","Reyes Jimenez-Aparicio","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Dipanwita", "last" : "Das"}, {"first" : "Thomas Michael", "last" : "Scherer"}, {"first" : "Amit", "last" : "Das"}, {"first" : "Tapan Kumar", "last" : "Mondal"}, {"first" : "Shaikh M.", "last" : "Mobin"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Jose Luis", "last" : "Priego"}, {"first" : "Reyes", "last" : "Jimenez-Aparicio"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "41","number": "38","pages": "11675--11683","abstract": "The combination of two highly noninnocent ligands with a 3rd-row transition metal produces the title complex ion which was crystd. as [Os(Q)2(bpy)](ClO4)·C6H6 (Q = 4,6-di-tert-butyl-o-iminobenzoquinone, bpy = 2,2'-bipyridine) and could be structurally characterized to exhibit a tris-chelate situation at the metal with trans positioned N and cis positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q.bul.-)OsIII(Q.bul.-) can rationalize the obsd. S = 1/2 situation with ligand-centered resulting spin. Ligand-based spin is confirmed by DFT (calcd. spin populations Q: 1.113; Os: -0.113; bpy: 0.001) and is also apparent from the EPR signal (g1 1.981, g2 1.955, g3 1.803, Dg 0.178, 〈g〉 1.915) which is influenced by the high spin-orbit coupling const. of the Os center. The susceptibility measurements reveal antiferromagnetic behavior. A 1-electron oxidn. and two 1-electron redns. could be monitored spectroelectrochem. (UV-visible-NIR) and analyzed by TD-DFT, in comparison with the results from the Ru analog. The anal. reflects the strong orbital mixing between the metal and the two Q-ligand MOs. [on SciFinder(R)]", "issn" : "1477-9226", "doi" : "10.1039/c2dt30903c", "bibtexKey": "Das.2012g" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/269d09befddee12ebe0844cb2911ae0ef/huebleriac", "tags" : [ "DFT","complex","complex;dinuclear","crystal","dinuclear","electrochem","electrochem;quinaldato","electrochem;quinolinecarboxylato","electronic","picolinato","prepn","quinaldato","quinolinecarboxylato","ruthenium","structure","tetrakispyridylpyrazine" ], "intraHash" : "69d09befddee12ebe0844cb2911ae0ef", "interHash" : "ce53dd1e5b734e7f31b9611cf636e468", "label" : "Carboxylate Tolerance of the Redox-Active Platform [Ru(m-tppz)Ru]n, where tppz = 2,3,5,6-Tetrakis(2-pyridyl)pyrazine, in the Electron-Transfer Series [(L)ClRu(m-tppz)RuCl(L)]n, n = 2+, +, 0, -, and 2-, with 2-Picolinato, Quinaldato, and 8-Quinolinecarboxylato Ligands (L-)", "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": "2010", "url": "", "author": [ "Tanaya Kundu","Biprajit Sarkar","Tapan Kumar Mondal","Jan Fiedler","Shaikh M. Mobin","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Tanaya", "last" : "Kundu"}, {"first" : "Biprajit", "last" : "Sarkar"}, {"first" : "Tapan Kumar", "last" : "Mondal"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Shaikh M.", "last" : "Mobin"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "49","number": "14","pages": "6565--6574","abstract": "The neutral title complexes [(L1-3)ClRuII(m-tppz)RuIICl(L1-3)] [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine with L1 = 2-picolinate (1), L2 = 2-quinolinecarboxylate (quinaldate) (2) and with the hitherto little used L3 = 8-quinolinecarboxylate (3)] were structurally characterized as approx. anti- (1 and 3) and syn-configured isomers (2) with L ligand N (1 and 3) or O atoms (2) trans to the pyrazine N atoms of tppz. In contrast to 1 and 2 with five-membered chelate rings, complex 3 (which is isomeric with 2) contains six-membered chelate rings. Each system 1-3 thus features a significantly different coordination situation, and all complexes exhibit a considerably distorted tppz bridge, including a twisted central pyrazine ring. In spite of this, double one-electron redn. of the bridge is always possible, as is evident from EPR and UV/visible spectroelectrochem. Two sep. (DE $\\sim$ 0.4 V and Kc $\\sim$ 107) 1-electron oxidns. occur on the metals, producing invariably EPR-silent (4 K) RuIIIRuII intermediates with moderately intense near-IR absorptions, ranging from 1500 to 1900 nm. IR spectroelectrochem. of the carboxylato carbonyl stretching bands did not result in any noticeable shift, in contrast to what was obsd. with dipyridyl ketones and related coligands. D. functional theory (DFT)/time-dependent DFT calcns. confirm the exptl. structures and explain the noted spectroscopic trends: destabilized and closer-spaced frontier orbitals for 3 over 2, with the comparison to 1 suggesting that the configuration is a major factor. Nevertheless, the rather unperturbed electronic structure of the [Ru(m-tppz)Ru]n entity, despite different coordination situations at the metal sites, is remarkable and suggests further use of this entity as a robust, carboxylate-tolerant redox-active platform in extended frameworks. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic100500p", "bibtexKey": "Kundu.2010" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2d93a351cbf2cd7378a923d4141a353a5/huebleriac", "tags" : [ "Carbenes","Carbenes;isolation","DFT","ESR","Germanium","acyclic","cyclicAlkylamino","radical","stabilized","transient" ], "intraHash" : "d93a351cbf2cd7378a923d4141a353a5", "interHash" : "6f9a0d63bff80ebb3016d356c59494fc", "label" : "Isolation of Transient Acyclic Germanium(I) Radicals Stabilized by Cyclic Alkyl(amino) Carbenes", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 5, "pub-type": "article", "journal": "Journal of the American Chemical Society", "year": "2019", "url": "", "author": [ "Mujahuddin M. Siddiqui","Samir Kumar Sarkar","Soumen Sinhababu","Paul Niklas Ruth","Regine Herbst-Irmer","Dietmar Stalke","Munmun Ghosh","Mingxing Fu","Lili Zhao","David Casanova","Gernot Frenking","Brigitte Schwederski","Wolfgang Kaim","Herbert W. Roesky" ], "authors": [ {"first" : "Mujahuddin M.", "last" : "Siddiqui"}, {"first" : "Samir Kumar", "last" : "Sarkar"}, {"first" : "Soumen", "last" : "Sinhababu"}, {"first" : "Paul Niklas", "last" : "Ruth"}, {"first" : "Regine", "last" : "Herbst-Irmer"}, {"first" : "Dietmar", "last" : "Stalke"}, {"first" : "Munmun", "last" : "Ghosh"}, {"first" : "Mingxing", "last" : "Fu"}, {"first" : "Lili", "last" : "Zhao"}, {"first" : "David", "last" : "Casanova"}, {"first" : "Gernot", "last" : "Frenking"}, {"first" : "Brigitte", "last" : "Schwederski"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Herbert W.", "last" : "Roesky"} ], "volume": "141","number": "5","pages": "1908--1912","abstract": "Despite the notable progress in the stabilization of main group radicals by NHCs and cyclicalkyl(amino) carbenes (cAACs), no germanium radicals have been isolated so far due to synthetic challenges. Stabilization of neutral [:EIR].bul. (E = Si, Ge) radicals is an uphill task, as these reactive transient species are highly susceptible to dimerization. Herein, we report the synthesis of acyclic neutral germanium(I) radicals Cy-cAAC:GeN(SiMe3)Dip I (1) and Me-cAAC:GeN(SiPh3)Mes II (2) obtained by the redn. of [Ar(SiR3)NGeCl3] with KC8 in the presence of cAAC. Compds. 1 and 2 are well characterized by single crystal X-ray structural anal., cyclic voltammetry, and EPR spectroscopy. Furthermore, the structure and bonding of compds. 1 and 2 have been investigated by theor. methods. [on SciFinder(R)]", "issn" : "0002-7863", "doi" : "10.1021/jacs.8b13434", "bibtexKey": "Siddiqui.2019" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/25ef1839f0429637d0dada95c2a501180/huebleriac", "tags" : [ "DFT","HOMO","LUMO","bathochromic","bipyridine","cationic","charge","chloro","complex","complex;DFT","cyclopentadienyl","diazabutadiene","hypsochromic","interaction","iridium","shift;orbital","transfer" ], "intraHash" : "5ef1839f0429637d0dada95c2a501180", "interHash" : "96bc57f69f317aeaebbcec6deeaf001e", "label" : "Replacement of 2,2'-Bipyridine by 1,4-Diazabutadiene Acceptor Ligands: Why the Bathochromic Shift for [(NN̂)IrCl(C5Me5)]+ Complexes but the Hypsochromic Shift for (NN̂)Ir(C5Me5)?", "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": "2003", "url": "", "author": [ "Stanislav Zalis","Monika Sieger","Stefan Greulich","Hermann Stoll","Wolfgang. Kaim" ], "authors": [ {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Monika", "last" : "Sieger"}, {"first" : "Stefan", "last" : "Greulich"}, {"first" : "Hermann", "last" : "Stoll"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "42","number": "17","pages": "5185--5191","abstract": "Replacement of 2,2'-bipyridine (bpy) by substituted 1,4-diazabutadiene (R-DAB) a-diimine ligands NN̂ leads to a substantial hypsochromic shift of $\\sim$0.8 eV for the long-wavelength absorption band in (NN̂)Ir(C5Me5) but to a bathochromic absorption shift of $\\sim$0.4 eV for [(NN̂)IrCl(C5Me5)]+. DFT calcns. on model complexes based on exptl. (R-DAB compds.) and geometry-optimized structures (bpy systems) reveal that the low-energy transitions of the cationic chloro complexes are largely of ligand-to-ligand charge-transfer character L'LCT (L = a-diimine, L' = Cl) whereas the neutral compds. exhibit p $\\rightarrow$ p* transitions between the considerably mixed metal dp and a-diimine p* orbitals. The much more pronounced metal-ligand orbital interaction for the R-DAB complexes causes the qual. different shifts on replacing the stronger basic bpy by the better p-acceptors R-DAB. Only the LUMO of the neutral compds. is destabilized on replacement of bpy by R-DAB whereas the LUMO of [(NN̂)IrCl(C5R'5)]+ and both HOMOs are stabilized through this change. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic034464k", "bibtexKey": "Zalis.2003" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/26b2350a0685e35b430ad8c347c803563/huebleriac", "tags" : [ "DFT","DMSO","NMR","NOESY","aryl","complex","complex;diaryl","complex;platinum","conformer","crystal","dimethyl","multinuclear","platinum","prepn","spectra;mol","structure","sulfoxide" ], "intraHash" : "6b2350a0685e35b430ad8c347c803563", "interHash" : "19c820d26cc0ceff01a54b09ed09672a", "label" : "Multiple Isomerism (cis/trans; syn/anti) in [(dmso)2Pt(aryl)2] Complexes: A Combined Structural, Spectroscopic, and Theoretical Investigation", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 4, "pub-type": "article", "journal": "Organometallics", "year": "2005", "url": "", "author": [ "Axel Klein","Thilo Schurr","Axel Knoedler","Dietrich Gudat","Karl-Wilhelm Klinkhammer","Vimal K. Jain","Stanislav Zalis","Wolfgang. Kaim" ], "authors": [ {"first" : "Axel", "last" : "Klein"}, {"first" : "Thilo", "last" : "Schurr"}, {"first" : "Axel", "last" : "Knoedler"}, {"first" : "Dietrich", "last" : "Gudat"}, {"first" : "Karl-Wilhelm", "last" : "Klinkhammer"}, {"first" : "Vimal K.", "last" : "Jain"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "24","number": "17","pages": "4125--4131","abstract": "The occurrence of cis or trans configurations in square planar diarylbis(DMSO)platinum(II) complexes with S-bonded DMSO ligands and aryl = 2,3,4,5,6-pentamethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2-, 3-, and 4-methylphenyl, and Ph has been investigated by multinuclear (1H, 13C, and 195Pt) NMR spectroscopy and crystal structure anal. Both methods confirm the cis configuration for complexes with the smaller Ph and methylphenyl (tolyl) ligands and the trans configuration for the compds. with the bulkier ligands, starting from 2,6-dimethylphenyl. Spectroscopic criteria could thus be established to identify configurational isomers. For the 2-tolyl complex an addnl. kind of isomerism arises from the relative orientation of the two Me substituents on the same side (syn) or on different sides of the coordination plane (anti). 2D-NMR spectroscopy allowed us to identify the conformers and to study isomerization mechanisms. DFT calcn. results agree well with the exptl. structures and with the spectroscopic data. [on SciFinder(R)]", "issn" : "0276-7333", "doi" : "10.1021/om050076", "bibtexKey": "Klein.2005" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2797a3057a11a46c48741553acbc5c966/huebleriac", "tags" : [ "DFT","MO;imidazolylketone","MO;optimized","arene","chlorocymeneosmium","crystal","cymene","fluorophosphate;mol","imidazolylglyoxal","imidazolylketone","mol","osmium","prepn","reaction","spectroelectrochem","structure","voltammetry" ], "intraHash" : "797a3057a11a46c48741553acbc5c966", "interHash" : "4de3d887f889ea3db00822fed936c25e", "label" : "Organoosmium complexes of imidazole-containing chelate acceptor ligands", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Inorganica Chimica Acta", "year": "2010", "url": "", "author": [ "Orkan Sarper","Biprajit Sarkar","Jan Fiedler","Falk Lissner","Wolfgang. Kaim" ], "authors": [ {"first" : "Orkan", "last" : "Sarper"}, {"first" : "Biprajit", "last" : "Sarkar"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Falk", "last" : "Lissner"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "363","number": "12","pages": "3070--3077","abstract": "[(L)Os(h6-Cym)Cl](PF6), Cym = p-cymene and L = bis(1-methylimidazol-2-yl)ketone (bik) or bis(1-methylimidazol-2-yl)glyoxal (big), were obtained and characterized with respect to spectroscopy, crystal structure (big complex) and spectroelectrochem. behavior at variable temps. DFT calcns. confirm the structure of [(big)Os(h6-Cym)Cl]+ with imidazolyl-N-bonded Os(II) in a boat-shaped seven-membered chelate ring with small N-Os-N angles (\\textless84°). Redn. of this compd. proceeds reversibly to a neutral complex of the a-semidione radical anion ligand big·-; EPR and IR spectroelectrochem. indicate very little participation from the heavy metal in the spin distribution. The analogous [(bik)Os(h6-Cym)Cl]+ could not be reduced reversibly to the ketyl radical complex but displayed a more reversible oxidn. at high potential. [on SciFinder(R)]", "issn" : "0020-1693", "doi" : "10.1016/j.ica.2010.04.007", "bibtexKey": "Sarper.2010" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2dbd231e499cd0f6b76ac86d22a1d9965/huebleriac", "tags" : [ "DFT","calcn","cobalt","complex","complex;nitrosylcobalt","crystal","diazabutadiene","electronic","ground","mol","nitrosyl","prepn","state","structure" ], "intraHash" : "dbd231e499cd0f6b76ac86d22a1d9965", "interHash" : "006c59fa137d82e8aa397c63b1b1dbb0", "label" : "Geometrical and ground state electronic structures of nitrosylcobalt complexes [(RNCHCHNR)Co(NO)(CO)] (R = isopropyl, 2,6-diisopropylphenyl or p-tolyl) from experiment and DFT-calculations", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Zeitschrift fuer Anorganische und Allgemeine Chemie", "year": "2002", "url": "", "author": [ "Monika Sieger","Klaus Hubler","Thomas Scheiring","Torsten Sixt","Stanislav Zalis","Wolfgang. Kaim" ], "authors": [ {"first" : "Monika", "last" : "Sieger"}, {"first" : "Klaus", "last" : "Hubler"}, {"first" : "Thomas", "last" : "Scheiring"}, {"first" : "Torsten", "last" : "Sixt"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "628","number": "11","pages": "2360--2364","abstract": "(RN:CHCH:NR)Co(NO)(CO), R = iso-Pr (1), 2,6-diisopropylphenyl (2) and p-tolyl (3), were synthesized and spectroscopically characterized. Compds. 1 and 2 could be crystd. for x-ray structure anal., CO/NO disorder was obsd. for 1. The results indicate a negligible amt. of charge transfer from the Co(NO)(CO) moiety to the 1,4-diazabutadiene acceptor ligands in the ground state, in agreement with DFT calcns. on 1 and as similarly reported for related 1,4-diaza-1,3-butadiene complexes of Ni(CO)2 and Fe(NO)2. [on SciFinder(R)]", "issn" : "0044-2313", "doi" : "10.1002/1521-3749(200211)628:11\\textless2360::AID-ZAAC2360\\textgreater3.0.CO;2-L", "bibtexKey": "Sieger.2002" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2f2bf57e917d809bbeb82b933ff28a7d0/huebleriac", "tags" : [ "DFT","EPR","acetylacetonate","acetylacetonate;ruthenium","complex","crystal","electrochem","hexatrieneazothiocarbonyl","magnetism","prepn","ruthenium","structure" ], "intraHash" : "f2bf57e917d809bbeb82b933ff28a7d0", "interHash" : "08d3e67f5d08e1f83fb6a9e95a54b44a", "label" : "Metal-Induced Thiophene Ring Opening and C-C Bond Formation To Produce Unique Hexa-1,3,5-trienediyl-Coupled Non-Innocent Ligand Chelates", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 4, "pub-type": "article", "journal": "Chemistry - A European Journal", "year": "2015", "url": "", "author": [ "Fabian Ehret","Martina Bubrin","Stanislav Zalis","Jose Luis Priego","Reyes Jimenez-Aparicio","Wolfgang. Kaim" ], "authors": [ {"first" : "Fabian", "last" : "Ehret"}, {"first" : "Martina", "last" : "Bubrin"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Jose Luis", "last" : "Priego"}, {"first" : "Reyes", "last" : "Jimenez-Aparicio"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "21","number": "43","pages": "15163--15166","abstract": "Ring opening of thiophenes contg. an azo function in 2-position and subsequent dimerization through C-C coupling were obsd. on reaction with [Ru(acac)2(CH3CN)2] (acac=acetylacetonate) to produce two 1,3,5-hexatriene-linked redox-active azothiocarbonyl chelate systems. Interaction of the non-innocent chelate ligands and of the metals at a nanoscale distance of 1.45 nm via the conjugated hexatriene bridge was studied by magnetic and electron spectroscopic measurements in conjunction with DFT calcns., revealing four-center magnetic interactions of this unique setting and weak intervalence coupling after redn. [on SciFinder(R)]", "issn" : "0947-6539", "doi" : "10.1002/chem.201502748", "bibtexKey": "Ehret.2015b" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/29c53c19f86a5da69772d6c7937e56d24/huebleriac", "tags" : [ "DFT","carbonyl","charge","complex","crystal","diazabutadiene","diimine","halide","oxidn","prepn","pseudohalide","redn","rhenium","spectroelectrochem","structure","transfer;rhenium" ], "intraHash" : "9c53c19f86a5da69772d6c7937e56d24", "interHash" : "350f4aa82b2134b371b77d2907d2f55a", "label" : "Oxidation and reduction response of a-diimine complexes with tricarbonylrhenium halides and pseudohalides", "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 Organometallic Chemistry", "year": "2014", "url": "", "author": [ "Anita Grupp","Martina Bubrin","Fabian Ehret","Hana Kvapilova","Stanislav Zalis","Wolfgang. Kaim" ], "authors": [ {"first" : "Anita", "last" : "Grupp"}, {"first" : "Martina", "last" : "Bubrin"}, {"first" : "Fabian", "last" : "Ehret"}, {"first" : "Hana", "last" : "Kvapilova"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "751","pages": "678--685","abstract": "Compds. [Re(CO)3X(R-DAB)], X = Cl, Br, CN, NCS and R-DAB = RN=CH-CH=NR (R = tert-butyl) were obtained, structurally characterized, and studied with regard to their oxidn. and redn. behavior using cyclic voltammetry, EPR, IR and UV-visible-NIR spectroelectrochem. Whereas the halide compds. exhibit more reversible oxidn. processes, the pseudohalide complexes display reversible one-electron redn., but irreversible oxidn. DFT and TD-DFT calcns. were employed to confirm the exptl. derived electronic structures and spectral properties. [on SciFinder(R)]", "doi" : "10.1016/j.jorganchem.2013.08.030", "bibtexKey": "Grupp.2014b" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2c2619af4498d85461f5495f0fc5cc840/huebleriac", "tags" : [ "DFT","EPR","bipyrimidine","complex","electrochem","isomerism","multifrequency","nitro","nitrosyl","prepn","redn;conformational","redox","ruthenium","system","system;spectroelectrochem","terpyridine" ], "intraHash" : "c2619af4498d85461f5495f0fc5cc840", "interHash" : "d4ec00b684d1b5d33ff248e3b2f94627", "label" : "Spectroelectrochemistry and DFT Analysis of a New RuNOn Redox System with Multifrequency EPR Suggesting Conformational Isomerism in the RuNO7 State", "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": "2007", "url": "", "author": [ "Priti Singh","Jan Fiedler","Stanislav Zalis","Carole Duboc","Mark Niemeyer","Falk Lissner","Thomas Schleid","Wolfgang. Kaim" ], "authors": [ {"first" : "Priti", "last" : "Singh"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Carole", "last" : "Duboc"}, {"first" : "Mark", "last" : "Niemeyer"}, {"first" : "Falk", "last" : "Lissner"}, {"first" : "Thomas", "last" : "Schleid"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "46","number": "22","pages": "9254--9261","abstract": "[Ru(NO)(bpym)(terpy)](PF6)3, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2''-terpyridine, with a RuNO6 configuration (angle Ru-N-O 175.2(4)°) was obtained from the structurally characterized precursor [Ru(NO2)(bpym)(terpy)](PF6), which shows bpym-centered redn. and metal-centered oxidn., as evident from EPR spectroscopy. The relatively labile [Ru(NO)(bpym)(terpy)]3+, which forms a structurally characterized MeCN substitution product [Ru(MeCN)(bpym)(terpy)](PF6)2 upon treatment with MeOH/MeCN, is electrochem. reduced in 3 1-electron steps of which the 3rd, leading to neutral [Ru(NO)(bpym)(terpy)], involves electrode adsorption. The 1st-two redn. processes cause shifts of n(NO) from 1957 via 1665 to 1388 cm-1, implying a predominantly NO-centered electron addn. UV-visible-NIR Spectroscopy shows long-wavelength ligand-to-ligand charge transfer absorptions for [RuII(NO-1)(bpym)(terpy)]+ in the visible region, whereas the paramagnetic intermediate [Ru(NO)(bpym)(terpy)]2+ exhibits no distinct absorption max. \\textgreater309 nm. EPR spectroscopy of the latter at 9.5, 95, and 190 GHz shows the typical invariant pattern of the RuNO7 configuration; however, the high-frequency measurements at 4 and 10 K reveal a splitting of the g1 and g2 components, which is tentatively attributed to conformers resulting from the bending of RuNO. DFT calcns. support the assignments of oxidn. states and the general interpretation of the electronic structure. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic701206a", "bibtexKey": "Singh.2007" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2e802c161b7cc45f2657ed131de6edf11/huebleriac", "tags" : [ "DFT","DMSO","calcn","complex","crystal","electrochem","electronic","oxidophenalenone","prepn","ruthenium","structure","structure;ruthenium","trithiacyclononane" ], "intraHash" : "e802c161b7cc45f2657ed131de6edf11", "interHash" : "3c9b8bdfbc47392b13d0dee1b89f0242", "label" : "Bidirectional non-innocence of the b-diketonato ligand 9-oxidophenalenone (L-) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Dalton Transactions", "year": "2014", "url": "", "author": [ "Hemlata Agarwala","Thomas Michael Scherer","Shaikh M. Mobin","Wolfgang Kaim","Goutam Kumar. Lahiri" ], "authors": [ {"first" : "Hemlata", "last" : "Agarwala"}, {"first" : "Thomas Michael", "last" : "Scherer"}, {"first" : "Shaikh M.", "last" : "Mobin"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Goutam Kumar.", "last" : "Lahiri"} ], "volume": "43","number": "10","pages": "3939--3948","abstract": "[RuII([9]aneS3)(L)(DMSO)]ClO4 ([1]ClO4) ([9]aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, DMSO = DMSO) was structurally characterized to reveal almost equal C-O bond distances of coordinated L-, suggesting a delocalized bonding situation of the b-diketonato ligand. The DMSO ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as was revealed by x-ray crystallog. and by DFT calcns. Cyclic voltammetry of 1+ exhibits two close-lying 1-electron oxidn. waves at 0.77 V and 0.94 V, and two similarly close 1-electron redn. processes at -1.43 V and -1.56 V vs. SCE in CH2Cl2. The electronic structures of 1n in the accessible redox states were analyzed via expts. (EPR and UV-visible-NIR spectroelectrochem.) and by DFT/TD-DFT calcns., revealing the potential for bidirectional noninnocent behavior of coordinated L·/-/·2-. Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidn. and redn. processes: [([9]aneS3)(DMSO)RuIII-L·]3+ (13+) .dblharw. [([9]aneS3)(DMSO)RuIII-L-]2+/[([9]aneS3)(DMSO)RuII-L·]2+ (12+) .dblharw. [([9]aneS3)(DMSO)RuII-L-]+ (1+) .dblharw. [([9]aneS3)(DMSO)RuII-L·2-] (1) .dblharw. [([9]aneS3)(DMSO)RuII-L3-]-/[([9]aneS3)(DMSO)RuI-L·2-]- (1-). [on SciFinder(R)]", "issn" : "1477-9226", "doi" : "10.1039/c3dt53069h", "bibtexKey": "Agarwala.2014" } ] }