{ "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" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/9c72c82a74d50a713d49e015053c4b74/droessler", "tags" : [ "amnesty","digital","group","human","international","malware","map","nso","pegasus","rights","violations" ], "intraHash" : "9c72c82a74d50a713d49e015053c4b74", "label" : "Digital Violence: How the NSO Group Enables State Terror", "user" : "droessler", "description" : "Forensic Architecture\u2019s Digital Violence investigation is a multidimensional study of the global use of the malware Pegasus made by Israeli cyber-surveillance company NSO Group.", "date" : "2023-03-18 11:43:59", "changeDate" : "2023-03-18 11:44:33", "count" : 1, "url" : "https://digitalviolence.org/#/" } , { "type" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/ba7b28d6e64d1f4ff7be8d105733ca65/droessler", "tags" : [ "BISAC","Book","Group","Industry","Study","classification","metadata","metadaten","publishing","scientific","tu9_monos" ], "intraHash" : "ba7b28d6e64d1f4ff7be8d105733ca65", "label" : "Complete BISAC Subject Headings List, 2021 Edition", "user" : "droessler", "description" : "Book Industry Study Group", "date" : "2022-12-01 18:36:37", "changeDate" : "2022-12-01 17:49:46", "count" : 1, "url" : "https://bisg.org/page/bisacedition" } , { "type" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/f7695077fd022b94368426149b834dde/droessler", "tags" : [ "deutschland","dokumentenserver","dspace","german","group","konsortium","repositorium","repository","software","user" ], "intraHash" : "f7695077fd022b94368426149b834dde", "label" : "German DSpace User Group - DSpace - LYRASIS Wiki", "user" : "droessler", "description" : "DSpace-Konsortium", "date" : "2020-08-06 12:01:49", "changeDate" : "2020-08-06 10:01:49", "count" : 1, "url" : "https://wiki.lyrasis.org/display/DSPACE/German+DSpace+User+Group" } , { "type" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/e97eb71284e4c5d166bbaeafe095cc4c/droessler", "tags" : [ "biologie","biology","etc","group","klima","monitoring","nachhaltigkeit","politik","synthetic","synthetische","tracking","umwelt","ökologie" ], "intraHash" : "e97eb71284e4c5d166bbaeafe095cc4c", "label" : "ETC Group | monitoring power, tracking technology, strengthening diversity", "user" : "droessler", "description" : "ETC Group works to address the socioeconomic and ecological issues surrounding new technologies that could have an impact on the world\u2019s poorest and most vulnerable people. ", "date" : "2018-08-09 23:13:04", "changeDate" : "2018-08-09 21:15:40", "count" : 1, "url" : "http://www.etcgroup.org/" } , { "type" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/e7834454ec54d0ca31dfb2caed1156c0/diglezakis", "tags" : [ "RDF","SemanticWeb","ShEx","community","group","metadata" ], "intraHash" : "e7834454ec54d0ca31dfb2caed1156c0", "label" : "Shape Expressions Community Group", "user" : "diglezakis", "description" : "", "date" : "2018-04-10 12:45:18", "changeDate" : "2018-04-10 10:45:18", "count" : 1, "url" : "https://www.w3.org/community/shex/" } , { "type" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/9329ad35c7f22930648fd40c97b420db/droessler", "tags" : [ "access","association","data","eua","european","expert","group","management","open","research","science","university" ], "intraHash" : "9329ad35c7f22930648fd40c97b420db", "label" : "EUA: European University Association - open science", "user" : "droessler", "description" : "Open Science: EUA discusses big deal negotiations, text and data mining and open data", "date" : "2017-10-18 14:30:21", "changeDate" : "2017-10-18 12:30:21", "count" : 1, "url" : "http://www.eua.be/activities-services/news/newsitem/2017/01/26/open-science-eua-discusses-big-deal-negotiations-text-and-data-mining-and-open-data" } , { "type" : "Bookmark", "id" : "https://puma.ub.uni-stuttgart.de/url/6506fd45137df41b323d9bb340328a07/droessler", "tags" : [ "group","iag","literaturlisten","numeric","puma","research","stuttgart","uni" ], "intraHash" : "6506fd45137df41b323d9bb340328a07", "label" : "Numerics Research Group | New numerical methods, analysis, efficient implementations, multi-scale problems, high performance computing", "user" : "droessler", "description" : "", "date" : "2016-01-15 10:13:04", "changeDate" : "2016-01-15 09:13:04", "count" : 1, "url" : "https://nrg.iag.uni-stuttgart.de/" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/26a5e962f82c75788dfa615ef68ed419c/slegewie", "tags" : [ "Acid,","Alternative","Analysis,","Base","Binding","Cells,","Exons,","F-H,","Group","HEK293","Heterogeneous-Nuclear","Humans,","Introns,","Kinases,","Linear","MCF-7","Mas,","Models,","Mutagenesis,","Mutation,","Neoplasms,","Nucleic","Protein-Tyrosine","Proteins,","Proto-Oncogene","RNA","RNA-Binding","Receptor","Regulatory","Ribonucleoprotein","Sequence","Sequence,","Sequences,","Sites,","Splicing," ], "intraHash" : "6a5e962f82c75788dfa615ef68ed419c", "interHash" : "e8adf17ba8666d4a803d7d7d88a2433b", "label" : "Decoding a cancer-relevant splicing decision in the RON proto-oncogene using high-throughput mutagenesis", "user" : "slegewie", "description" : "", "date" : "2025-03-05 15:52:38", "changeDate" : "2025-03-05 15:52:38", "count" : 1, "pub-type": "article", "journal": "Nature Communications", "year": "2018", "url": "", "author": [ "Simon Braun","Mihaela Enculescu","Samarth T. Setty","Mariela Cortés-López","Bernardo P. de Almeida","F. X. Reymond Sutandy","Laura Schulz","Anke Busch","Markus Seiler","Stefanie Ebersberger","Nuno L. Barbosa-Morais","Stefan Legewie","Julian König","Kathi Zarnack" ], "authors": [ {"first" : "Simon", "last" : "Braun"}, {"first" : "Mihaela", "last" : "Enculescu"}, {"first" : "Samarth T.", "last" : "Setty"}, {"first" : "Mariela", "last" : "Cortés-López"}, {"first" : "Bernardo P.", "last" : "de Almeida"}, {"first" : "F. X. Reymond", "last" : "Sutandy"}, {"first" : "Laura", "last" : "Schulz"}, {"first" : "Anke", "last" : "Busch"}, {"first" : "Markus", "last" : "Seiler"}, {"first" : "Stefanie", "last" : "Ebersberger"}, {"first" : "Nuno L.", "last" : "Barbosa-Morais"}, {"first" : "Stefan", "last" : "Legewie"}, {"first" : "Julian", "last" : "König"}, {"first" : "Kathi", "last" : "Zarnack"} ], "volume": "9","number": "1","pages": "3315","abstract": "Mutations causing aberrant splicing are frequently implicated in human diseases including cancer. Here, we establish a high-throughput screen of randomly mutated minigenes to decode the cis-regulatory landscape that determines alternative splicing of exon 11 in the proto-oncogene MST1R (RON). Mathematical modelling of splicing kinetics enables us to identify more than 1000 mutations affecting RON exon 11 skipping, which corresponds to the pathological isoform RON∆165. Importantly, the effects correlate with RON alternative splicing in cancer patients bearing the same mutations. Moreover, we highlight heterogeneous nuclear ribonucleoprotein H (HNRNPH) as a key regulator of RON splicing in healthy tissues and cancer. Using iCLIP and synergy analysis, we pinpoint the functionally most relevant HNRNPH binding sites and demonstrate how cooperative HNRNPH binding facilitates a splicing switch of RON exon 11. Our results thereby offer insights into splicing regulation and the impact of mutations on alternative splicing in cancer.", "language" : "eng", "pmid" : "30120239", "file" : "Volltext:C\\:\\\\Users\\\\SL\\\\Zotero\\\\storage\\\\29LKX6JF\\\\Braun et al. - 2018 - Decoding a cancer-relevant splicing decision in the RON proto-oncogene using high-throughput mutagen.pdf:application/pdf", "issn" : "2041-1723", "pmcid" : "PMC6098099", "doi" : "10.1038/s41467-018-05748-7", "bibtexKey": "braun_decoding_2018" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2e19714157a37841e8da3b967e0e473be/ferrangiones", "tags" : [ "Group","Investment","decision","making," ], "intraHash" : "e19714157a37841e8da3b967e0e473be", "interHash" : "4b8d7ce928a279043732cbfd908b2778", "label" : "Using Fuzzy-TOPSIS Method to Rank Investors\u2019 Decision Variables in Venture Proposals Evaluation", "user" : "ferrangiones", "description" : "", "date" : "2024-07-02 11:28:25", "changeDate" : "2024-07-02 11:28:25", "count" : 1, "pub-type": "conference", "year": "2016", "url": "http://www.esade.edu/research-webs/eng/grec/news-events/83rd-ewg-mcda", "author": [ "Ferran Giones","David Riu","Xari Rovira" ], "authors": [ {"first" : "Ferran", "last" : "Giones"}, {"first" : "David", "last" : "Riu"}, {"first" : "Xari", "last" : "Rovira"} ], "note": "83rd Meeting of Euro Working Group on MCDA ; Conference date: 31-03-2016 Through 01-04-2016","abstract": "Understanding the criteria used by investors to evaluate new ventures\u2019 proposals remains an active area of research in entrepreneurship (Nunes et al. 2014). Prior research identifies that there are differences in the types and importance of criteria used to evaluate venture proposals (Streletzki & Schulte 2013), and suggests that in some cases just a few element define the criteria used to make investment decisions (Maxwell et al. 2011). Despite scholars\u2019 interest in understanding the evaluation criteria it is still remains unclear the criteria and order of importance (Franke et al. 2008; Nunes et al. 2014).We propose a method based on Fuzzy Order Preference by Similarity to an Ideal Solution (Fuzzy TOPSIS) to help entrepreneurs to analyze the evaluation, in terms of fuzzy opinions, of new ventures proposals. To this end a set of fuzzy linguistic terms based on triangular fuzzy numbers are considered.A group of investment experts has been considered to assess different factors and variables by means of linguistic terms with different levels of precision. Results provide not only a ranked list of variables obtained from the group of experts\u2019 opinion buy also a measure of the consensus reaches. A real example is presented to show the real applicability and efficiency of the proposed methodology.", "language" : "English", "bibtexKey": "e9fbc011d8934cdbb8f563b83605ae1f" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/23f9f3e787df9dcbe363a2b39322f6f4c/jmueller", "tags" : [ "(Architekt),","(Architekt,","(renewable),","Aktivhaus,","Baden-Württemberg,","Batteriespeicher,","Bauen,","Baugeschichte,","Bundesrepublik,","Corbusier","Daten(technisch),","Denkmalpflege,","Deutschland,","Electro","Elektromobilität,","Energie(erneuerbar),","Energiedach,","Energiekonzept,","Energieverbrauch,","Energieversorgung,","Experimentalhaus,","Flachdach,","Forschungsprojekt,","Grid,","Group","Heritage","Home,","Ingenieur),","Ingenieur,","Jeanneret,","Le","Modulbauweise,","Montage,","Mustersiedlung,","Neues","PV","PV-Anlage,","Pierre","Planer),","Plusenergiehaus,","Site,","Smart","Sobek","Sobek,","Solarthermie,","Stadtquartier,","Steuerungstechnik,","Stuttgart(11),","TGA,","Trägerrost,","Vacuum","Vakuumisolationspaneel,","Vorfertigung,","WSGreen","Weissenhof","Weißenhofsiedlung,","Weltkulturerbe,","Werner","World","assembly,","beam","building","care","concept,","construction,","consumption,","control","data(technical),","energy","estate,","experimental","flat","grid,","grillage,","history,","home,","house,","isolation","mobility,","model","modular","monuments,","new","of","panel,","plus","prefabrication,","project,","quarter,","quarters,","research","roof,","solar","supply,","system,","technology,","the","thermics,","town","twenties," ], "intraHash" : "3f9f3e787df9dcbe363a2b39322f6f4c", "interHash" : "a5ab8d242238cc8dbe9dbef1415050fb", "label" : "Das Prinzip der Schwesterlichkeit - Mitversorgung von Denkmälern durch Plusenergiegebäude", "user" : "jmueller", "description" : "", "date" : "2023-11-27 15:10:57", "changeDate" : "2023-11-27 15:10:57", "count" : 1, "pub-type": "incollection", "booktitle": "Denkmal und Energie 2018: Energieeffizienz, Nachhaltigkeit und Nutzerkomfort","publisher":"Springer Vieweg","address":"Wiesbaden", "year": "2017", "url": "https://doi.org/10.1007/978-3-658-19672-1_7", "author": [ "Marc-Steffen Fahrion","Kurt Denzel","Werner Sobek" ], "authors": [ {"first" : "Marc-Steffen", "last" : "Fahrion"}, {"first" : "Kurt", "last" : "Denzel"}, {"first" : "Werner", "last" : "Sobek"} ], "editor": [ "Bernhard Weller","Sebastian Horn" ], "editors": [ {"first" : "Bernhard", "last" : "Weller"}, {"first" : "Sebastian", "last" : "Horn"} ], "pages": "79--92","abstract": "Die Stuttgarter Weißenhofsiedlung wurde als Wegbereiter des Internationalen Stils weltberühmt. Am 17. Juli 2016 wurden zwei Häuser der Siedlung, das Einfamilienhaus und das Doppelhaus der Architekten Le Corbusier und Pierre Jeanneret, Teil des UNESCO Weltkulturerbes [1,2]. Die Mustersiedlung bestand ursprünglich aus 21 Experimentalbauten, von denen 10, als Folge des Zweiten Weltkriegs, verloren gingen [3].", "isbn" : "978-3-658-19671-4", "bibtexKey": "fahrion_prinzip_2017" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/24ba9517baebb943ae3a6b3887f6c7ba9/droessler", "tags" : [ "amnesty","apple","group","international","klage","menschenrechte","nso","pegasus","software","spionage","überwachung" ], "intraHash" : "4ba9517baebb943ae3a6b3887f6c7ba9", "interHash" : "ca9fcce8e91d04db92b67db0abea6ef9", "label" : "Pressemeldung: Apple verklagt NSO Group, um den Missbrauch durch staatlich geförderte Spionagesoftware einzuschränken", "user" : "droessler", "description" : "", "date" : "2022-07-26 10:18:57", "changeDate" : "2022-07-26 08:20:17", "count" : 1, "pub-type": "electronic", "year": "2021", "url": "https://www.apple.com/de/newsroom/2021/11/apple-sues-nso-group-to-curb-the-abuse-of-state-sponsored-spyware/", "editor": [ " Apple" ], "editors": [ {"first" : "", "last" : "Apple"} ], "bibtexKey": "apple2022pressemeldung" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/20f40a77fe96947fad5e59587f36f3740/huebleriac", "tags" : [ "4","anion;ESR","chelate","chelate;electron","chelate;homolysis","diazabutadiene","diazabutadiene;methyl","diazabutadiene;platinum","electrochem","group","mesityl","methyl","organoplatinum","photochem","platinum","radical","radical;photohomolysis","redn","transfer" ], "intraHash" : "0f40a77fe96947fad5e59587f36f3740", "interHash" : "56b06388224c0dc3784900a4204d16c5", "label" : "EPR study of electron transfer and group transfer in organoplatinum(II) and (IV) compounds", "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 Chemical Society, Perkin Transactions 2: Physical Organic Chemistry", "year": "1997", "url": "", "author": [ "Axel Klein","Steffen Hasenzahl","Wolfgang. Kaim" ], "authors": [ {"first" : "Axel", "last" : "Klein"}, {"first" : "Steffen", "last" : "Hasenzahl"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "number": "12","pages": "2573--2577","abstract": "Chelate complexes between the 1,4-diazabuta-1,3-diene ligands RN:CHCH:NR = R-DAB (R = alkyl, aryl) and the organoplatinum fragments PtMe2, PtMe4 and PtMes2 (Mes = mesityl) can be reversibly reduced to paramagnetic compds., formulated as Pt(II) or (IV) species bound by radical anion ligands (R-DAB.bul.-). EPR studies in fluid and frozen soln. support this assignment; however, the metal contribution to the singly occupied MO is higher for the paramagnetic PtII species than for the PtIV systems. Comparison with related radical complexes of the main group and transition element series reveals that even the organoplatinum(IV) compds. exhibit a relatively high degree of ligand-to-metal spin transfer as evident from small 1H(CH) and large 14N and 195Pt EPR hyperfine coupling consts. The tetramethylplatinum(IV) complexes are photoreactive; a Pt-contg. primary dissocn. product from Pt-C s bond homolysis was detected by EPR spectroscopy using tBu-NO as a spin trap reagent during irradn. Group transfer reactivity also was noted for radical anions where the conversion [(R-DAB)PtMe2].bul.- $\\rightarrow$ [(R-DAB)PtMe4].bul.- could be monitored by EPR spectroscopy. [on SciFinder(R)]", "issn" : "0300-9580", "bibtexKey": "Klein.1997" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/279cdb9a98a8b1b6241ccb64026794c8b/huebleriac", "tags" : [ "carbonyl","complex","complex;electrooxidn","complex;electroredn","complex;palladium","crystal","diphosphinoquinoxaline","group","platinum","prepn","structure","structure;platinum","structure;rhenium" ], "intraHash" : "79cdb9a98a8b1b6241ccb64026794c8b", "interHash" : "9917f8ec8515ccfa875cb20958263a80", "label" : "Structures and redox properties of metal complexes of the electron-deficient diphosphine chelate ligand R,R-quinoxP", "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": "2008", "url": "", "author": [ "Atanu Kumar Das","Ece Bulak","Biprajit Sarkar","Falk Lissner","Thomas Schleid","Mark Niemeyer","Jan Fiedler","Wolfgang. Kaim" ], "authors": [ {"first" : "Atanu Kumar", "last" : "Das"}, {"first" : "Ece", "last" : "Bulak"}, {"first" : "Biprajit", "last" : "Sarkar"}, {"first" : "Falk", "last" : "Lissner"}, {"first" : "Thomas", "last" : "Schleid"}, {"first" : "Mark", "last" : "Niemeyer"}, {"first" : "Jan", "last" : "Fiedler"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "27","number": "2","pages": "218--223","abstract": "The air-stable chiral diphosphine chelate ligand R,R-qinoxP (L; 2,3-bis(tert-butylmethylphosphino)quinoxaline) as developed by Imamoto et al. (2005). L was used to obtain the crystallog. characterized complexes (L)PtCl2 (1), (L)PdCl2 (2), and (L)Re(CO)3Cl (3). Coordination occurs via the P donor atoms, as indicated by crystal structures and NMR studies; the quinoxaline N donors do not participate in any coordination to the metals. The stereochem. arrangements obsd. illustrate the enantioselectivity reported for catalysis involving complexes of L. Electron acceptance by the quinoxaline heterocycle is responsible not only for the improved stability of L toward air but also for rather facile redn. of the complexes to the persistent radical anions 1·-and 3·- In contrast, the redn. to 2·- proceeds irreversibly even at 243 K in the absence of excess chloride. EPR, UV-vis, and IR spectroelectrochem. was used, when possible, to establish the spin location in the quinoxaline p system with rather small contributions from the metals or the P nuclei. [on SciFinder(R)]", "issn" : "0276-7333", "doi" : "10.1021/om700755y", "bibtexKey": "Das.2008" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/24f6433f1ea46898fc234a4249fcfb849/huebleriac", "tags" : [ "Group","VIB","basicity","bidiazine","bidiazine;Group","bidiazine;bipyrazine","bidiazine;electron","bidiazine;molybdenum","bidiazine;redox","bidiazine;tungsten","carbonyl","carbonyl;bipyridazine","carbonyl;bipyrimidine","carbonyl;chromium","configuration","potential" ], "intraHash" : "4f6433f1ea46898fc234a4249fcfb849", "interHash" : "3efa3bf4b2b2a9ad87713cc0b5dd3acf", "label" : "Coordination characteristics of four isomeric a-diimine ligands. p Molecular orbital perturbation calculations for the bidiazines and their correlation with the properties of group 6 metal carbonyl complexes", "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": "1986", "url": "", "author": [ "Sylvia Ernst","Wolfgang. Kaim" ], "authors": [ {"first" : "Sylvia", "last" : "Ernst"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "108","number": "13","pages": "3578--3586","abstract": "Energies and charge distributions of the lower unoccupied p MO's were detd. for the isomeric bidiazine ligands 3,3'-bipyridazine (bpdz), 4,4'-bipyrimidine (bpm), 2,2'-bipyrazine (bpz), and 2,2'-bipyrimidine (bpym) as well as for 2,2'-bipyridine (bpy) by Gueckel MO perturbation calcns. In conjunction with exptl. pKa values, the calcn. results are related to the different stabilities, redox potentials, and various spectroscopic properties of Cr, Mo, and W tetracarbonyl complexes with these ligands. W(CO)5L (L = bpdz, bpm) were isolated as intermediates in the reactions between W(THF)(CO)5 and L.. Each of the 4 isomeric ligands exhibits very characteristic features, and the potential uses of the individual systems for different purposes in coordination chem. are discussed. Whereas bpdz is the strongest base in that series, thus compensating for a rather high-lying p* level, the bpm complexes exhibit the strongest back-bonding interaction because of a very low-lying p* level and sufficient ligand basicity. The bpz system is distinguished by acquiring high amts. of addnl. charge at both sets of N centers upon redn., and finally, the otherwise less outstanding bpym ligand is unique among the bidiazine isomers by forming binuclear bischelate complexes on 2nd coordination. [on SciFinder(R)]", "issn" : "0002-7863", "doi" : "10.1021/ja00273a005", "bibtexKey": "Ernst.1986b" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2e66e3f6c255933e8a07cff4565c504df/huebleriac", "tags" : [ "Group","VIB","anion;molybdenum","bipyrimidine","carbonyl","carbonyl;ESR","radical","substitution","tributylphosphine" ], "intraHash" : "e66e3f6c255933e8a07cff4565c504df", "interHash" : "89d779412465b6d16be7335a534843e7", "label" : "Mono- and binuclear tri- and tetracarbonyl complexes of chromium(0), molybdenum(0), and tungsten(0) with the 2,2'-bipyrimidine radical anion", "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": "1984", "url": "", "author": [ "Wolfgang. Kaim" ], "authors": [ {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "23","number": "21","pages": "3365--3368","abstract": "[((CO)4M)x bpym]-. (x = 1, 2; M = Cr, Mo, W; bpym = 2,2'-bipyrimidine) were studied by high-resoln. ESR. The unpaired electron resides predominantly in the LUMO of the heterocycle; HMO-McLachlan calcns. were used to interpret the hyperfine coupling consts. [((CO)4Mo)2bpym]- underwent successive replacement of 2 axial CO groups by PBu3. A p*/s* hyperconjugation model accounted for the facile CO substitution and for the spin transfer to the peripheral 31P nuclei. An unexpected behavior was found for the g values of the complexes, which were generally lower than the g of the free ligand. This result points to a strong contribution from a low-lying electronically excited state to the radical ground state. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic00189a019", "bibtexKey": "Kaim.1984h" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2dd46420ded7276f8b1fe5f6a1f5c2fbe/huebleriac", "tags" : [ "Group","VIB","bipyridine","bipyrimidine","bipyrimidine;bipyrimidine","bipyrimidine;chromium","bipyrimidine;tungsten","carbonyl","carbonyl;molybdenum","carbonyl;redox","electrochem","metal","ruthenium","ruthenium;carbonyl","transition" ], "intraHash" : "dd46420ded7276f8b1fe5f6a1f5c2fbe", "interHash" : "a7fdf3b06bd5b5af5d5653c78b31ab31", "label" : "Ambidentate ligand with high p-acceptor capacity: D6-metal complexes of 4,4'-bipyrimidine", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Angewandte Chemie", "year": "1985", "url": "", "author": [ "Sylvia Ernst","Wolfgang. Kaim" ], "authors": [ {"first" : "Sylvia", "last" : "Ernst"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "97","number": "5","pages": "431--433","abstract": "M(CO)5(THF) (M = Cr, Mo, W), Ru(bpy)2Cl2 (bpy = 2,2'-bipyridine), and RuCl2(DMSO)4 reacted with 4,4'-bipyrimidine (L) to give M(CO)4L, [Ru(bpy)2L](PF6)2, and [RuL3](PF6)2, resp. [W(CO)5]2L, that was prepd. from W(CO)5(THF) and L (2:1 ratio), under reflux was converted to W(CO)4L. The redox potentials are obtained for M(CO)4L, [Ru(bpy)2L](PF6)2, and [W(CO)5]2L. For [RuL3](PF6)2 the elec. potentials were obtained for the Ru3+/Ru2+, Ru2+/Ru+, Ru+/Ru0, and Ru0/Ru- couples. The complexes were characterized by IR, electronic, NMR, and ESR spectra. [on SciFinder(R)]", "issn" : "0044-8249", "bibtexKey": "Ernst.1985" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2704ea00c19a09a11422b8a0e260199ab/huebleriac", "tags" : [ "8","ESR","ESR;osmium","ESR;ruthenium","Group","complex","complex;iron","cyano","nitrosyl","prepn" ], "intraHash" : "704ea00c19a09a11422b8a0e260199ab", "interHash" : "d9ad95bebcf24d1735c80352fb999e8d", "label" : "EPR Characteristics of the [(NC)5M(NO)]3- Ions (M = Fe, Ru, Os). Experimental and DFT Study Establishing NO.bul. as a 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": "2001", "url": "", "author": [ "Matthias Wanner","Thomas Scheiring","Wolfgang Kaim","Leonardo D. Slep","Luis M. Baraldo","Jose A. Olabe","Stanislav Zalis","Evert Jan. Baerends" ], "authors": [ {"first" : "Matthias", "last" : "Wanner"}, {"first" : "Thomas", "last" : "Scheiring"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Leonardo D.", "last" : "Slep"}, {"first" : "Luis M.", "last" : "Baraldo"}, {"first" : "Jose A.", "last" : "Olabe"}, {"first" : "Stanislav", "last" : "Zalis"}, {"first" : "Evert Jan.", "last" : "Baerends"} ], "volume": "40","number": "22","pages": "5704--5707","abstract": "K2[(NC)5Ru(NO)] was prepd. from K4[Ru(CN)6] and KNO2 and converted to (NEt4)2[(NC)5Ru(NO)]. The g factor components of [(NC)5M(NO)]3- (M = Fe, Ru, Os) were calcd. by relativistic d. functional calcns., including spin-orbit coupling. The calcd. values are in good agreement with previous (M = Fe) and new exptl. results (M = Ru, Os). Spin-orbit coupling effects are particularly strong for the osmium system. Whereas MII-NO· is the most appropriate formulation describing the spin distribution, there is substantial contribution (ca. 25 \\% ) from the metal to the singly occupied MO in each case. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic010452s", "bibtexKey": "Wanner.2001b" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/210481207494b1ba280cd180c99a8061c/huebleriac", "tags" : [ "ESR","VIB","benzo","benzochalcogenadiazole;oxadiazole","carbonyl","carbonyl;selenadiazole","carbonyl;sulfadiazole","group" ], "intraHash" : "10481207494b1ba280cd180c99a8061c", "interHash" : "a128bb71df3a8eb5a649f9460f9bc689", "label" : "Heterocyclic radical anions as ligands: An unexpected coordination change in pentacarbonylmetal complexes", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Angewandte Chemie", "year": "1982", "url": "", "author": [ "Wolfgang Kaim","Volker. Kasack" ], "authors": [ {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Volker.", "last" : "Kasack"} ], "volume": "94","number": "9","pages": "712--713","abstract": "M(CO)6 (M = Cr, W, Mo) react in THF with the radical anion I to give [(CO)5M]2L-. (M = Cr, Mo; L = I; X = O, S, Se; M = W; X = O, S) and (CO)5WL-. (X = Se). In [(CO)5W]L-., L is coordinated to W through the Se atom. The complexes were detected by ESR spectra. [on SciFinder(R)]", "issn" : "0044-8249", "bibtexKey": "Kaim.1982c" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/25056e1fad6ccf8772eaa446088a4cf10/huebleriac", "tags" : [ "Group","VIB","carbonyl","chem","chromium","complex;ESR","complex;tungsten","cyanopyridine","cyanopyridine;molybdenum","electrochem","electroredn","electroredn;cyanopyridine","electroredn;redn","pentacarbonyl","redn","redn;electroredn" ], "intraHash" : "5056e1fad6ccf8772eaa446088a4cf10", "interHash" : "d86f453cd52b5ebeb4eac3a93ee78896", "label" : "Chemical and electrochemical reduction of pentacarbonyl(4-cyanopyridine) complexes of chromium(0), molybdenum(0) and tungsten(0)", "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": "1984", "url": "", "author": [ "Wolfgang. Kaim" ], "authors": [ {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "23","number": "4","pages": "504--506","abstract": "The complexes [LM(CO)5] (L = 4-cyanopyridine and M = Cr, Mo, W) were reduced by K in THF and at a glassy C electrode in DMF. The resulting radical anion complexes [LM(CO)5]-. were also obtained from replacement reactions of the metal hexacarbonyls with the ligand radical anion L-. or via electron transfer from decacarbonyldimetalates to the free ligand L. The radical complexes were characterized by high resoln. ESR. The unpaired electron resides predominately in the heterocyclic ligand; only minor perturbations of spin distribution occur via the metal fragments. The results are related to the MLCT features in the electronic spectra of these complexes. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic00172a025", "bibtexKey": "Kaim.1984l" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2529101a4172189cb17f695b98d19fa6a/huebleriac", "tags" : [ "Group","Main","electron","hydride","induced","light","review;organometallic","review;review","transfer" ], "intraHash" : "529101a4172189cb17f695b98d19fa6a", "interHash" : "d0a47103745051ef54f2baa4aba17a17", "label" : "Thermal and light induced electron transfer reactions of Main Group metal hydrides and organometallics", "user" : "huebleriac", "description" : "", "date" : "2022-06-15 11:26:56", "changeDate" : "2022-06-15 09:26:56", "count" : 3, "pub-type": "article", "journal": "Topics in Current Chemistry", "year": "1994", "url": "", "author": [ "Wolfgang. Kaim" ], "authors": [ {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "169","number": "Electron Transfer I","pages": "231--251","abstract": "A review with \\textgreater143 refs. [on SciFinder(R)]", "issn" : "0340-1022", "bibtexKey": "Kaim.1994c" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/232ee25b910134ec22e13a1b299291934/huebleriac", "tags" : [ "Group","MO","VIB","azobipyridine","bipyrimidine","bischelant","carbonyl;Group","carbonyl;MO","carbonyl;electronic","carbonyl;energy","electrochem","electrochem;bipyrimidine","electrochem;electrochem","electrochem;pyridyltetrazine","level","pyridylpyrazine","pyridyltetrazine;pyridylpyrazine","transition" ], "intraHash" : "32ee25b910134ec22e13a1b299291934", "interHash" : "6939cad18951d07991ceb8002a8240c6", "label" : "Four bridging bis chelate ligands with very low lying p* orbitals. MO perturbation calculations, electrochemistry, and spectroscopy of mononuclear and binuclear group 6 metal tetracarbonyl complexes", "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": "1987", "url": "", "author": [ "Wolfgang Kaim","Stephan. Kohlmann" ], "authors": [ {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Stephan.", "last" : "Kohlmann"} ], "volume": "26","number": "1","pages": "68--77","abstract": "Coordination characteristics of the 4 bridging, p-delocalized bis chelate ligands 2,2'-bipyrimidine (bpym), 2,5-bis(2-pyridyl)pyrazine (bppz), 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), and azo-2,2'-bipyridine (abpy) were evaluated with use of p MO perturbation calcns. and were studied exptl. by example of mononuclear and binuclear complexes with the fragments M(CO)4 (M = Cr, Mo, W). The substantial stabilization of the p* (LUMO) levels in the order bpym, bppz, bptz, abpy strongly facilitates redn. of the complexes and causes shifts of the intense metal-to-ligand charge-transfer (LMCT) absorption bands out into the near-IR region. Despite a notable activation barrier for the formation of binuclear abpy complexes with 6-coordinate metals, (abpy)[Mo(CO)4]2 was prepd. and it exhibits most remarkable spectral properties such as an intense yet rather narrow and solvent-insensitive MLCT absorption band at 11,000 cm-1, another detectable absorption max. \\textgreater30,000 cm-1, a redn. potential close to that of the ref. electrode, SCE, and closely spaced yet well-resolved CO stretching frequencies in the IR spectrum. All these spectral results can be correlated to p MO calcn. data, which strongly suggest the use of bptz and abpy for studies concerned with ligand-mediated electronic interactions between metal centers. A particular asset of binuclear abpy complexes is the unusually short metal-metal distance caused by their coordination-induced S-frame conformation. [on SciFinder(R)]", "issn" : "0020-1669", "doi" : "10.1021/ic00248a016", "bibtexKey": "Kaim.1987g" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2bf63a6fdb9108e06bac398d785826dc1/huebleriac", "tags" : [ "Group","VIB","chalcogen","crystal","heterocubane","heterocubane;IR","heterocubane;redox","heterocubane;rhenium","potential","prepn;UV","rhenium","structure" ], "intraHash" : "bf63a6fdb9108e06bac398d785826dc1", "interHash" : "c0144b52936af0cda691842d656e365f", "label" : "Heterocubane cluster compounds (NEt4)Y:M[(μ3-S)Re(CO)3]3(μ3-E) (M = W or Mo, Y = O or S, E = S or Se). Structures, spectroscopy, and electrochemistry", "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": "2001", "url": "", "author": [ "Fridmann Hornung","Matthias Wanner","Karl Wilhelm Klinkhammer","Wolfgang Kaim","Jan. Fiedler" ], "authors": [ {"first" : "Fridmann", "last" : "Hornung"}, {"first" : "Matthias", "last" : "Wanner"}, {"first" : "Karl Wilhelm", "last" : "Klinkhammer"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Jan.", "last" : "Fiedler"} ], "volume": "627","number": "10","pages": "2430--2444","abstract": "Thiometalates [MS4]2- (M = Mo, W) or [WOS3]2- react with Re(CO)5(O3SCF3) and Li2E (E = S or Se) to yield the following compds. which were structurally characterized: (NEt4)S:W[(μ3-S)Re(CO)3]3(μ3-S)(NEt4) (I), (NEt4)O/S:W[(μ3-S)Re(CO)3](μ3-S)(NEt4) (I/II), (mixed crystals), (NEt4)S:W[(μ3-S)Re(CO)3]3(μ3-Se)(NEt4) (III) and (NEt4)S:Mo[(μ3-S)Re(CO)3]3(μ3-S)(NEt4) (IV). The heterocubane anions I-IV contain electron-rich centers such as Re(I) or sulfide whereas Mo(VI) or W(VI) act as acceptor sites. Accordingly, the absorption spectra show long-wavelength metal-to-ligand charge transfer transitions, and cyclic voltammetry reveals a quasi-reversible redn. of the clusters. Although both 6-coordinate Re(I) and 4-coordinate metal(VI) centers are present in the clusters there is no evidence for significant metal-to-metal charge transfer interaction. [on SciFinder(R)]", "issn" : "0044-2313", "bibtexKey": "Hornung.2001" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2a0d4754e323ee2654314c671a25866ed/huebleriac", "tags" : [ "Group","VIB","bipyridazine","bipyridazine;UV","carbonyl" ], "intraHash" : "a0d4754e323ee2654314c671a25866ed", "interHash" : "aa400c38b2d878e625188dbcab47cfbf", "label" : "3,3'-Bipyridazine: The 'second-best' bidiazine ligand for metal carbonyl M(CO)4 fragments (M = chromium, molybdenum, tungsten)", "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": "1986", "url": "", "author": [ "Sylvia Ernst","Wolfgang. Kaim" ], "authors": [ {"first" : "Sylvia", "last" : "Ernst"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "114","number": "2","pages": "123--125","abstract": "Owing to its relatively high basicity (pKa1 = 3.37), 3,3'-bipyridazine (L) yields M(CO)4L (M = Cr, Mo, W) which have both metal-to-ligand charge transfer absorption max. at longer wavelengths than corresponding 2,2'-bipyrimidine and 2,2'-bipyrazine compds. After 4,4'-bipyramidine, 3,3'-bipyridazine is the 2nd-best p acceptor among the sym. bidiazines with a-diamine structure. Redox potentials were detd. [on SciFinder(R)]", "issn" : "0020-1693", "doi" : "10.1016/S0020-1693(00)86442-7", "bibtexKey": "Ernst.1986" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2c3c002a97349095657b9182fd041c278/huebleriac", "tags" : [ "Group","complex","ligand","main","metal","nitrogen","paramagnetic","review","review;paramagnetic","transition" ], "intraHash" : "c3c002a97349095657b9182fd041c278", "interHash" : "4f4adab9c4241864caa5c6dcbe4fe453", "label" : "Paramagnetic main Group and transition metal complexes containing unsaturated nitrogen ligands", "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 Library", "year": "1990", "url": "", "author": [ "Wolfgang Kaim","Barbara. Olbrich-Deussner" ], "authors": [ {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Barbara.", "last" : "Olbrich-Deussner"} ], "volume": "22","number": "Organomet. Radical Processes","pages": "173--200","abstract": "A review with 164 refs. [on SciFinder(R)]", "issn" : "0378-5203", "bibtexKey": "Kaim.1990e" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2f4d1a9bb83f927f31ed652370f78e63e/huebleriac", "tags" : [ "Group","VIB","carbonyl","chalcogenadiazole","chalcogenadiazole;selenadiazole","chromium","complex","complex;Group","complex;oxadiazole","complex;quinoxaline","complex;redn","complex;thiadiazole","complex;tungsten","potential","quinoxaline;molybdenum","tungsten" ], "intraHash" : "f4d1a9bb83f927f31ed652370f78e63e", "interHash" : "a0e5ceb623890f399b7b52fdfe7371e9", "label" : "2-Heteroatom-1,3-diazoles and quinoxaline as bridging p-acceptor ligands for Group VIB metal carbonyl fragments M(CO)5 (M = Cr, Mo, W). Synthesis, electrochemistry, absorption and emission spectroscopy", "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": "1989", "url": "", "author": [ "Wolfgang Kaim","Stephan Kohlmann","Alistair J. Lees","Mthembeni. Zulu" ], "authors": [ {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "Stephan", "last" : "Kohlmann"}, {"first" : "Alistair J.", "last" : "Lees"}, {"first" : "Mthembeni.", "last" : "Zulu"} ], "volume": "575","pages": "97--114","abstract": "M(CO)5L (M = Cr, Mo, W; L = 2,1,3-benzoxadiazole (bod), 2,1,3-benzothiadiazole (btd), 2,1,3-benzoselenadiazole (bsd)), [M1(CO)5]2L1 (M1 = Cr, W; L1 = bod, btd, bsd, quinoxaline, 2,1,3-thiadiazole) were prepd. and characterized by cyclic voltammetry, UV-visible adsorption and emission spectroscopy. The complexes exhibit low-lying metal-to-ligand charge transfer (MLCT, d $\\rightarrow$ p*) transitions as evident from long wavelength absorptions and are easily reduced to yield persistent anion radicals. [W(CO)5]2L1 (L1 = btd, bsd) show weak near IR (\\textgreater750 nm) emission from rather short-lived MLCT excited states. While quinoxaline and monocyclic 2,1,3-thiadiazole also form binuclear W(CO)5 complexes, the related 2-methyl-1,2,3-benzotriazole does not bind W(CO)5 fragments in the neutral state but only as the more basic anion radical as evident from ESR spectroscopy. [on SciFinder(R)]", "issn" : "0044-2313", "bibtexKey": "Kaim.1989" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/27710d451094991120cbf5e8998ea4d51/huebleriac", "tags" : [ "DFT","Group","IA","alkylation;magnesacarborane","calcn","calcn;mol","crystal","geometry","magnesacarborane;heterocarborane","magnesium","metal","metalation","metallacarborane","optimized","prepn","structure","substituted","substituted;DFT","trimethylsilyl" ], "intraHash" : "7710d451094991120cbf5e8998ea4d51", "interHash" : "2377abb8cc8cc5b2f0aeb71f97076b36", "label" : "Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 28. Selective Alkylation and Reactivity of \\dqCarbons Adjacent\\dq and \\dqCarbons Apart\\dq Tetracarba-nido-dodecaborane(12) Derivatives toward Group 1 and Group 2 Metals. Synthetic, Spectroscopic, and Structural Investigations on Lithium-, Sodium-, Potassium-, Cesium-, and Magnesium-Complexed C4B8 Carboranes", "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": "2000", "url": "", "author": [ "Narayan S. Hosmane","Hongming Zhang","John A. Maguire","Ying Wang","Temesgen Demissie","Thomas J. Colacot","Maria B. Ezhova","Kai-Juan Lu","Dunming Zhu","Thomas G. Gray","Sarah C. Helfert","Suneil N. Hosmane","Jess D. Collins","Frank Baumann","Wolfgang Kaim","William N. Lipscomb" ], "authors": [ {"first" : "Narayan S.", "last" : "Hosmane"}, {"first" : "Hongming", "last" : "Zhang"}, {"first" : "John A.", "last" : "Maguire"}, {"first" : "Ying", "last" : "Wang"}, {"first" : "Temesgen", "last" : "Demissie"}, {"first" : "Thomas J.", "last" : "Colacot"}, {"first" : "Maria B.", "last" : "Ezhova"}, {"first" : "Kai-Juan", "last" : "Lu"}, {"first" : "Dunming", "last" : "Zhu"}, {"first" : "Thomas G.", "last" : "Gray"}, {"first" : "Sarah C.", "last" : "Helfert"}, {"first" : "Suneil N.", "last" : "Hosmane"}, {"first" : "Jess D.", "last" : "Collins"}, {"first" : "Frank", "last" : "Baumann"}, {"first" : "Wolfgang", "last" : "Kaim"}, {"first" : "William N.", "last" : "Lipscomb"} ], "volume": "19","number": "4","pages": "497--508","abstract": "The carbons apart tetracarbon carborane nido-2,6-(R)2-4,12-(SiMe3)2-2,4,6,12-C4B8H8 [R = SiMe3 (I), Bu (II)] and several of its B-alkylated derivs. react with Mg metal in THF solvent to produce magnesacarboranes [e.g., (THF)2Mg(SiMe3)4(B-Bu-t)B4B7H7 (V)] in yields ranging from 57\\% to 74\\%. The magnesacarboranes were characterized by chem. anal. and IR and 1H, 11B, and 13C NMR spectroscopy and by single-crystal x-ray diffraction. Two types of cages were found, one in (THF)2Mg(SiMe3)4(B-Me)C4B7H7 (IV) and the other in (L)2Mg(SiMe3)2(R)2(B-Y)C4B7H7 [L = THF, R = SiMe3, Y = t-Bu (V); L = THF, R = SiMe3, Y = H (VI); (L)2 = TMEDA, R = Bu, Y = H (XI)]. Both cages showed electron-precise C and B atoms, as well as electron-deficient fragments. Approx. d. functional ab initio MO calcns. showed that the dianionic C4B8 cage can exist in a no. of energy-equiv. isomeric forms that can be trapped by a metal ion such as Mg. The reactions of I with the Group IA metals followed a different course in which two distinct steps occurred. The 1st step formed the paramagnetic intermediates which, in a slower step, reacted with a 2nd equiv. of the metal to give the diamagnetic [(SiMe3)4C4B8H8]2-. For the lighter metals, this dianion picked up a proton to give [(THF)4M][(SiMe3)4C4B8H9] [M = Li (VIII), Na (IX), K (X)] in 35-54\\% yield. In the case of Cs, no protonation occurred and the final product was a polymeric dicesiacarborane, [exo-Cs(TMEDA)-1-Cs-(SiMe3)4C4B8H8]n (VII), isolated in 41\\% yield. All were characterized by chem. anal. and IR and 1H, 11B, and 13C NMR spectroscopy; VII and VIII were addnl. characterized by single-crystal x-ray diffraction studies. In VIII-X the Group IA metal was solvated by four THF mols. and was not involved in the cage, while in VII one Cs occupied an apical position above a C3B3 open face of one carborane and bonded to a B3 face of a neighboring carborane. The 2nd Cs, solvated by a TMEDA mol., occupies an exo-polyhedral position and was not part of the polymeric chain. One carbons adjacent magnesacarborane, exo-(m-H)3Mg(THF)3(SiMe3)2(Me)2C4B8H8 (XII), was also synthesized, in 81\\% yield, by the reaction of the metal with the (SiMe3)2(Me)2C4B8H8 precursor. Single-crystal x-ray diffraction studies showed the compd. to be composed of an exo-polyhedral [Mg(THF)3]2+ that is loosely bound to a [(SiMe3)2(Me)2C4B8H8]2- cage. The carborane is best described as an 10-vertex arachno-(SiMe3)2C2B8H8 cage that subtends an electron-precise MeC:CMe fragment. [on SciFinder(R)]", "issn" : "0276-7333", "doi" : "10.1021/om990677z", "bibtexKey": "Hosmane.2000" } , { "type" : "Publication", "id" : "https://puma.ub.uni-stuttgart.de/bibtex/2dd247d6e4f6157daed586230a3310cbf/huebleriac", "tags" : [ "15","16","16;methide","Group","MO;MO","VA","VIA","affinity","electron","methide","methide;electron","spectra","transmission" ], "intraHash" : "dd247d6e4f6157daed586230a3310cbf", "interHash" : "7ea5294591d4c545467db27eed86711c", "label" : "Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzene", "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": "1985", "url": "", "author": [ "Judith C. Giordan","John H. Moore","John A. Tossell","Wolfgang. Kaim" ], "authors": [ {"first" : "Judith C.", "last" : "Giordan"}, {"first" : "John H.", "last" : "Moore"}, {"first" : "John A.", "last" : "Tossell"}, {"first" : "Wolfgang.", "last" : "Kaim"} ], "volume": "107","number": "20","pages": "5600--5604","abstract": "Electron-transmission spectroscopy was used to det. the energies of low-lying neg.-ion states of MenM (M = N, P, As, n = 3; M = O, S, n = 2) as well as p-(MenM)2C6H4 (M = N, As, n = 3; M = O, S, n = 2). Spectral peaks are obsd., corresponding to electron capture into benzene p* orbitals perturbed by interactions with the substituents and into substituent s* orbitals. N substituents give a substantial splitting and destabilization of the benzene LUMO (p4,5*), while P and As substituents cause little splitting and a slight stabilization of this orbital. Virtual orbital eigenvalues from min.-basis-set SCF-MO calcns. on the monosubstituted benzenes show the same trends. Redn. in the p character of the substituent lone pair, redn. in the magnitude of interactions, and increased stabilization of the benzene LUMO's by mixing with the substituent s* orbitals along the N $\\rightarrow$ As series may all contribute to this trend. Similarly, O substituents give a substantial p4*-p5* splitting while S substituents give primarily an inductive stabilization of the p4,5* orbitals. [on SciFinder(R)]", "issn" : "0002-7863", "doi" : "10.1021/ja00306a003", "bibtexKey": "Giordan.1985" } ] }