@article{LambertKauppSchleyer1993, author = {Lambert, Christoph and Kaupp, Martin and Schleyer, Paul von Rague}, title = {"Inverted" Sodium-Lithium Electronegativity: Polarity and Metalation Energies of Organic and Inorganic Alkali-Metal Compounds}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-60054}, year = {1993}, abstract = {No abstract available}, subject = {Anorganische Chemie}, language = {en} } @article{BraunschweigDewhurstSchwabetal.2010, author = {Braunschweig, Holger and Dewhurst, Rian D. and Schwab, Katrin and Wagner, Katharina}, title = {{N ',N ''-Bis[2,6-bis(1-methylethyl)phenyl]-N,N-dimethylguanidinato-kappa N-2 ',N ''}dibromidoborane}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-67622}, year = {2010}, abstract = {In the molecular structure of the title compound, C27H40N3BBr2, the B atom is connected to two bromide substituents and a guanidinate scaffold, forming a four- membered ring. An aryl group is connected to each N atom in the ring that contains two isopropyl groups in positions 2 and 6.}, subject = {Anorganische Chemie}, language = {en} } @article{TackeWuttkeHenke1992, author = {Tacke, Reinhold and Wuttke, F. and Henke, H.}, title = {Zur Stereochemie der mikrobiellen Reduktion von rac-Acetyl( t-butyl)methylphenylsilan mit Trigonopsis variabilis (DSM 70714) und Corynebacterium dioxydans (ATCC 21766): Aufkl{\"a}rung der absoluten Konfiguration der Biotransformationsprodukte (SiR,CR)- und ( SiS ,CR)-t-Butyl( 1-hydroxyethyl)methylphenylsilan}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-64176}, year = {1992}, abstract = {No abstract available}, subject = {Anorganische Chemie}, language = {en} } @article{ZhangRadackiBraunschweigetal.2021, author = {Zhang, Fangyuan and Radacki, Krzysztof and Braunschweig, Holger and Lambert, Christoph and Ravat, Prince}, title = {Zinc-[7]helicenocyanine and its discrete π-stacked homochiral Dimer}, series = {Angewandte Chemie International Edition}, volume = {60}, journal = {Angewandte Chemie International Edition}, doi = {10.1002/anie.202109380}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256534}, pages = {23656-23660}, year = {2021}, abstract = {In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10\(^6\) M\(^{-1}\) and 3.42×107 M\(^{-1}\) in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn\(^{-7}\)HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.}, language = {en} } @article{ScherpfSchwarzScharfetal.2018, author = {Scherpf, Thorsten and Schwarz, Christopher and Scharf, Lennart T. and Zur, Jana-Alina and Helbig, Andeas and Gessner, Viktoria H.}, title = {Ylide-Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis}, series = {Angewandte Chemie - International Edition}, volume = {57}, journal = {Angewandte Chemie - International Edition}, number = {39}, doi = {10.1002/anie.201805372}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-228551}, pages = {12859-12864}, year = {2018}, abstract = {Phosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross-coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron-rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide-functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.}, language = {en} } @article{RamlerKrummenacherLichtenberg2020, author = {Ramler, Jacqueline and Krummenacher, Ivo and Lichtenberg, Crispin}, title = {Well-Defined, Molecular Bismuth Compounds: Catalysts in Photochemically Induced Radical Dehydrocoupling Reactions}, series = {Chemistry - A European Journal}, volume = {26}, journal = {Chemistry - A European Journal}, number = {64}, doi = {10.1002/chem.202002219}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-224577}, pages = {14551 -- 14555}, year = {2020}, abstract = {A series of diorgano(bismuth)chalcogenides, [Bi(di-aryl)EPh], has been synthesised and fully characterised (E=S, Se, Te). These molecular bismuth complexes have been exploited in homogeneous photochemically-induced radical catalysis, using the coupling of silanes with TEMPO as a model reaction (TEMPO=(tetramethyl-piperidin-1-yl)-oxyl). Their catalytic properties are complementary or superior to those of known catalysts for these coupling reactions. Catalytically competent intermediates of the reaction have been identified. Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single-crystal X-ray diffraction analysis, and (TD)-DFT calculations.}, language = {en} } @phdthesis{Fritze2021, author = {Fritze, Lars}, title = {Ways to Novel Inorganic-Organic Hybrid Materials Applying New B-C Bond Formation Strategies}, doi = {10.25972/OPUS-24217}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-242173}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {π-Conjugated oligomers and polymers with tricoordinate boron centers incorporated into the main chain have attracted considerable attention as the interaction of the vacant p orbital on boron with an adjacent π system of the chain leads to conjugated materials with intriguing optical and electronic properties. This enables applicability in organic electronics and optoelectronics (OLEDs, OFETs, photovoltaics) or as sensory materials. The potential of our B-C coupling protocol using metal-free catalytic Si/B exchange condensation is demonstrated by the synthesis of a series of π-conjugated monodisperse (het)aryl oligoboranes. Variation of the (het)aryl moieties allowed for tunability of the optoelectronic properties of the materials. Additionally, catalytic C-C cross-coupling strategies were applied to synthesize oligofuryl-based mono- and bisboranes, as well as polymers. These studies led to very robust and highly emissive compounds (f up to 97 \%), which allow for tuning of their emission color from blue to orange. Furthermore, this work includes investigations of reaction routes to a kinetically stabilized tetraoxaporphyrinogen. Being a key aspect of this work, a full investigation of the mechanism of the catalytic Si/B exchange was carried out. Additionally, this work presents the use of borenium cations to perform B-C coupling via intermolecular electrophilic borylation. Similar to the Si/B exchange, this route is capable of giving access to diaryl(bromo)boranes.}, subject = {Konjugierte Polymere}, language = {en} } @article{MansourSteigerNageletal.2019, author = {Mansour, Ahmed M. and Steiger, Christoph and Nagel, Christoph and Schatzschneider, Ulrich}, title = {Wavelength-dependent control of the CO release kinetics of manganese(I) tricarbonyl PhotoCORMs with benzimidazole coligands}, series = {European Journal of Inorganic Chemistry}, volume = {2019}, journal = {European Journal of Inorganic Chemistry}, number = {42}, doi = {10.1002/ejic.201900894}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-218362}, pages = {4572-4581}, year = {2019}, abstract = {A series of photoactivatable CO-releasing molecules (PhotoCORMs) was prepared from manganese pentacarbonyl bromide and 1H-benzimidazol-2-ylmethyl-(N-phenyl)amine ligands (L) bearing different electron-donating and electron-withdrawing groups R = H, 4-CH\(_3\), 4-OCH\(_3\), 4-Cl, 4-NO\(_2\), 2-, 3-, and 4-COOCH\(_3\) on the phenyl substituent to give octahedral manganese(I) complexes of the general formula [MnBr(CO)\(_3\)(L)]. Aerated DMSO solutions of the compounds are stable in the dark for 16 h with no CO release. However, the compounds rapidly release CO upon illumination at 412-525 nm, depending on the substitution pattern. Its influence on the photophysical and photochemical properties was systematically explored using UV/Vis spectroscopy and CO release measurements with a commercial gas sensor system. In the nitro-substituted compound, the electronically excited state switched from benzimidazole- to phenyl-centered, leading to a markedly different photochemical behavior of this visible-light activated PhotoCORM.}, language = {en} } @phdthesis{Ramler2023, author = {Ramler, Jacqueline}, title = {Versatile Use of Neutral and Cationic Diorgano Bismuth Compounds: Ligation of Transition Metals, Lewis Acidity, Low Valent Species and Catalysis}, doi = {10.25972/OPUS-24054}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-240547}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2023}, abstract = {In der vorliegenden Arbeit wurden Diorganobismut-Spezies hinsichtlich ihrer Eigenschaften als Liganden in {\"U}bergangsmetallkomplexen, ihrer Lewis-Azidit{\"a}t, ihrer Eignung als Katalysatoren und die Generierung niedervalenter Spezies untersucht.}, subject = {Bismut}, language = {en} } @article{PlakhutinZhidomirovArbuznikov1992, author = {Plakhutin, B. N. and Zhidomirov, G. M. and Arbuznikov, Alexei V.}, title = {Vector coupling coefficients for calculations of transition-metal atoms and ions by the SCF coupling operator method}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-30702}, year = {1992}, abstract = {No abstract available}, language = {en} } @article{RiesAlbrightSilvestreetal.1986, author = {Ries, Wolfgang and Albright, Thomas and Silvestre, Jerome and Bernal, Ivan and Malisch, Wolfgang and Burschka, Christian}, title = {Unusual structural features of a siloxane}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-31925}, year = {1986}, abstract = {Crystals of the R, S diastereoisomer of [Cp(CO)\(_2\)-FeSiCH\(_3\)F]\(_2\)O are monoclinic, space group ndc (No. 14), with a = 846.0(3) [836.4(1»), b = 768.0(3) [757.1(1»), c = 1548.5(4) [1522.3(2)] pm, {3 = 97.34(3t [97.47(3t] at 300 K [120 K] with Z = 2. Even at 120 K the Si-O-Si fragment is found to be strictly linear due to crystallographically imposed symmetry. To explain the unusual electron distribution derived from the X-ray data collected, several types of possible disorders are discussed, none of which leads to a satisfying explanation. Retaining the Ci symmetry (linear Si-O-Si fragment in the final model) the important bond lengths are Fe-Si 226.7(1) [226.5(1)] pm, Si-F 160.9(2) [161.8(2)] pm, Si-O 160.3(1) [161.1(1)] pm, Si-C 185.0(3) [185.6(3)] pm. The electronic features of this compound were probed via molecular orbital calculations of the extended Hiickel type. It was found that the lone pairs on the siloxane oxygen were tipped away from cylindrical symmetry. The tipping was directed toward the fluorine substituents on the silicon atoms and away from the CpFe(CO)\(_2\) units. A pertubational approach was utilized to rationalize this effect.}, subject = {Chemie}, language = {en} } @unpublished{StennettMattockVollertetal.2018, author = {Stennett, Tom and Mattock, James and Vollert, Ivonne and Vargas, Alfredo and Braunschweig, Holger}, title = {Unsymmetrical, Cyclic Diborenes and Thermal Rearrangement to a Borylborylene}, series = {Angewandte Chemie, International Edition}, volume = {57}, journal = {Angewandte Chemie, International Edition}, doi = {10.1002/anie.201800671}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-160258}, pages = {4098-4102}, year = {2018}, abstract = {Cyclic diboranes(4) based on a chelating monoanionic, benzylphosphine linker were prepared by boron-silicon exchange between arylsilanes and B\(_2\)Br\(_4\). Coordination of Lewis bases to the remaining sp\(^2\) boron atom yielded unsymmetrical sp\(^3\)-sp\(^3\) diboranes, which were reduced with KC\(_8\) to their corresponding trans-diborenes. These compounds were studied by a combination of spectroscopic methods, X-ray diffraction and DFT calculations. PMe\(_3\)-stabilized diborene 6 was found to undergo thermal rearrangement to gem- diborene 8. DFT calculations on 8 reveal a polar boron-boron bond, and indicate that the compound is best described as a borylborylene.}, language = {en} } @article{ArrowsmithBoehnkeBraunschweigetal.2016, author = {Arrowsmith, Merle and B{\"o}hnke, Julian and Braunschweig, Holger and Celik, Mehmet and Dellermann, Theresa and Hammond, Kai}, title = {Uncatalyzed Hydrogenation of First-Row Main Group Multiple Bonds}, series = {Chemistry, A European Journal}, volume = {22}, journal = {Chemistry, A European Journal}, number = {48}, doi = {10.1002/chem.201604094}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-139364}, pages = {17169 -- 17172}, year = {2016}, abstract = {Room temperature hydrogenation of an SIDep-stabilized diboryne (SIDep = 1,3-bis(diethylphenyl)-4,5-dihydroimidazol-2-ylidene) and a CAAC-supported diboracumulene (CAAC = 1-(2,6- diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) provided the first selective route to the corresponding 1,2-dihydrodiborenes. DFT calculations showed an overall exothermic (ΔG = 19.4 kcal mol\(^{-1}\) two-step asynchronous H\(_2\) addition mechanism proceeding via a bridging hydride.}, subject = {Diborane}, language = {en} } @article{RamlerSchwarzmannStoyetal.2022, author = {Ramler, Jacqueline and Schwarzmann, Johannes and Stoy, Andreas and Lichtenberg, Crispin}, title = {Two Faces of the Bi-O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si-O Bond Formation}, series = {European Journal of Inorganic Chemistry}, volume = {2022}, journal = {European Journal of Inorganic Chemistry}, number = {7}, doi = {10.1002/ejic.202100934}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257428}, year = {2022}, abstract = {The diorgano(bismuth)alcoholate [Bi((C\(_{6}\)H\(_{4}\)CH\(_{2}\))\(_{2}\)S)OPh] (1-OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD-)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi-O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1-OPh has been investigated (TEMPO=(tetramethyl-piperidin-1-yl)-oxyl). Different reaction pathways can deliberately be addressed by applying photochemical or thermal reaction conditions and by choosing radical or closed-shell substrates (TEMPO vs. phenol). Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single-crystal X-ray diffraction analysis, and (TD)-DFT calculations.}, language = {en} } @article{SchmidtFantuzziKlopfetal.2021, author = {Schmidt, Paul and Fantuzzi, Felipe and Klopf, Jonas and Schr{\"o}der, Niklas B. and Dewhurst, Rian D. and Braunschweig, Holger and Engel, Volker and Engels, Bernd}, title = {Twisting versus delocalization in CAAC- and NHC-stabilized boron-based biradicals: the roles of sterics and electronics}, series = {Chemistry - A European Journal}, volume = {27}, journal = {Chemistry - A European Journal}, number = {16}, doi = {10.1002/chem.202004619}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256636}, pages = {5160-5170}, year = {2021}, abstract = {Twisted boron-based biradicals featuring unsaturated C\(_2\)R\(_2\) (R=Et, Me) bridges and stabilization by cyclic (alkyl)(amino)carbenes (CAACs) were recently prepared. These species show remarkable geometrical and electronic differences with respect to their unbridged counterparts. Herein, a thorough computational investigation on the origin of their distinct electrostructural properties is performed. It is shown that steric effects are mostly responsible for the preference for twisted over planar structures. The ground-state multiplicity of the twisted structure is modulated by the σ framework of the bridge, and different R groups lead to distinct multiplicities. In line with the experimental data, a planar structure driven by delocalization effects is observed as global minimum for R=H. The synthetic elusiveness of C\(_2\)R\(_2\)-bridged systems featuring N-heterocyclic carbenes (NHCs) was also investigated. These results could contribute to the engineering of novel main group biradicals.}, language = {en} } @unpublished{SchmidtFantuzziArrowsmithetal.2020, author = {Schmidt, Uwe and Fantuzzi, Felipe and Arrowsmith, Merle and Hermann, Alexander and Prieschl, Dominic and Rempel, Anna and Engels, Bernd and Braunschweig, Holger}, title = {Tuneable reduction of cymantrenylboranes to diborenes or borylene-derived boratafulvenes}, series = {Chemical Communications}, journal = {Chemical Communications}, doi = {10.1039/D0CC06398C}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-222149}, year = {2020}, abstract = {Whereas the reduction of N-heterocyclic carbene (NHC)-stabilised cymantrenyldibromoboranes, (NHC)BBr\(_2\)Cym, in benzene results in formation of the corresponding diborenes (NHC)\(_2\)B\(_2\)Cym\(_2\), a change of solvent to THF yields a borylene of the form (NHC)\(_2\)BCym, stabilised through its boratafulvene resonance form.}, language = {en} } @article{BrammerBlankeKellneretal.2022, author = {Brammer, Jan C. and Blanke, Gerd and Kellner, Claudia and Hoffmann, Alexander and Herres-Pawlis, Sonja and Schatzschneider, Ulrich}, title = {TUCAN: A molecular identifier and descriptor applicable to the whole periodic table from hydrogen to oganesson}, series = {Journal of Cheminformatics}, volume = {14}, journal = {Journal of Cheminformatics}, number = {1}, issn = {1758-2946}, doi = {10.1186/s13321-022-00640-5}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-299730}, year = {2022}, abstract = {TUCAN is a canonical serialization format that is independent of domain-specific concepts of structure and bonding. The atomic number is the only chemical feature that is used to derive the TUCAN format. Other than that, the format is solely based on the molecular topology. Validation is reported on a manually curated test set of molecules as well as a library of non-chemical graphs. The serialization procedure generates a canonical "tuple-style" output which is bidirectional, allowing the TUCAN string to serve as both identifier and descriptor. Use of the Python NetworkX graph library facilitated a compact and easily extensible implementation.}, language = {en} } @article{FoehrenbacherKrahfussZapfetal.2021, author = {F{\"o}hrenbacher, Steffen A. and Krahfuss, Mirjam J. and Zapf, Ludwig and Friedrich, Alexandra and Ignat'ev, Nikolai V. and Finze, Maik and Radius, Udo}, title = {Tris(pentafluoroethyl)difluorophosphorane: a versatile fluoride acceptor for transition metal chemistry}, series = {Chemistry Europe}, volume = {27}, journal = {Chemistry Europe}, number = {10}, doi = {10.1002/chem.202004885}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256665}, pages = {3504-3516}, year = {2021}, abstract = {Fluoride abstraction from different types of transition metal fluoride complexes [L\(_n\)MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C\(_2\)F\(_5\))\(_3\)PF\(_2\) to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C\(_2\)F\(_5\))\(_3\)PF\(_3\)]\(^-\)) is reported. (C\(_2\)F\(_5\))\(_3\)PF\(_2\) reacted with trans-[Ni(iPr\(_2\)Im)\(_2\)(Ar\(^F\))F] (iPr2Im=1,3-diisopropylimidazolin-2-ylidene; Ar\(^F\)=C\(_6\)F\(_5\), 1 a; 4-CF\(_3\)-C\(_6\)F\(_4\), 1 b; 4-C\(_6\)F\(_5\)-C\(_6\)F\(_4\), 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr\(_2\)Im)\(_2\)(solv)(Ar\(^F\))]FAP (2 a-c[solv]; solv=Et\(_2\)O, CH\(_2\)Cl\(_2\), THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh\(_3\), solvent coordination was suppressed and the complexes trans-[Ni(iPr\(_2\)Im)\(_2\)(PPh\(_3\))(C\(_6\)F\(_5\))]FAP (trans-2 a[PPh\(_3\)]) and cis-[Ni(iPr\(_2\)Im)\(_2\)(Dipp\(_2\)Im)(C\(_6\)F\(_5\))]FAP (cis-2 a[Dipp\(_2\)Im]) (Dipp\(_2\)Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp\(_2\)Im)CuF] (3) in CH\(_2\)Cl\(_2\) or 1,2-difluorobenzene led to the isolation of [{(Dipp\(_2\)Im)Cu}\(_2\)]\(^2\)\(^+\)2 FAP\(^-\) (4). Subsequent reaction of 4 with PPh\(_3\) and different carbenes resulted in the complexes [(Dipp\(_2\)Im)Cu(LB)]FAP (5 a-e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp\(_2\)Im)Cu(C\(_6\)Me\(_6\))]FAP (5 f), which serves as a source of [(Dipp\(_2\)Im)Cu)]\(^+\). Fluoride abstraction of [Cp\(_2\)TiF\(_2\)] (7) resulted in the formation of dinuclear [FCp\(_2\)Ti(μ-F)TiCp\(_2\)F]FAP (8) (Cp=η\(^5\)-C\(_5\)H\(_5\)) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.}, language = {en} } @article{FoehrenbacherZehKrahfussetal.2021, author = {F{\"o}hrenbacher, Steffen A. and Zeh, Vivien and Krahfuss, Mirjam J. and Ignat'ev, Nikolai V. and Finze, Maik and Radius, Udo}, title = {Tris(pentafluoroethyl)difluorophosphorane and N-Heterocyclic Carbenes: Adduct Formation and Frustrated Lewis Pair Reactivity}, series = {European Journal of Inorganic Chemistry}, volume = {2021}, journal = {European Journal of Inorganic Chemistry}, number = {20}, doi = {10.1002/ejic.202100183}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257386}, pages = {1941-1960}, year = {2021}, abstract = {The synthesis and characterization of Lewis acid/base adducts between tris(pentafluoroethyl)difluorophosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) and selected N-heterocyclic carbenes (NHCs) R\(_{2}\)Im (1,3-di-organyl-imidazolin-2-ylidene) and phosphines are reported. For NHCs with small alkyl substituents at nitrogen (R=Me, nPr, iPr) the adducts NHC ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) (2 a-h) were isolated. The reaction with the sterically more demanding NHCs Dipp\(_{2}\)Im (1,3-bis-(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene) (1 i) and tBu\(_{2}\)Im (1,3-di-tert-butyl-imidazolin-2-ylidene) (1 j) afforded the aNHC adducts 3 i and 3 j (a denotes "abnormal" NHC coordination via a backbone carbon atom). The use of tBuMeIm (1-tert-butyl-3-methyl-imidazolin-2-ylidene) (1 m) led to partial decomposition of the NHC and formation of the salt [tBuMeIm-H][MeIm ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)] (4 m). The phosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) forms adducts with PMe\(_{3}\) but does not react with PPh\(_{3}\) or PCy\(_{3}\). The mer-cis isomer of literature-known Me\(_{3}\)P ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) (5 a) was structurally characterized. Mixtures of the phosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) and the sterically encumbered NHCs tBu\(_{2}\)Im, Dipp\(_{2}\)Im, and Dipp\(_{2}\)Im\(^{H2}\) (1,3-bis-(2,6-di-iso-propylphenyl)-imidazolidin-2-ylidene) (1 k) showed properties of FLPs (Frustrated Lewis Pairs) as these mixtures were able to open the ring of THF (tetrahydrofuran) to yield NHC-(CH\(_{2}\))\(_{4}\)O-PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) 6 i-k. Furthermore, the deprotonation of the weak C-H acids CH\(_{3}\)CN, acetone, and ethyl acetate was achieved, which led to the formation of the corresponding imidazolium salts and the phosphates [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(CH\(_{2}\)CN)]\(^{-}\) (7), [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(OC(=CH\(_{2}\))CH\(_{3}\))]\(^{-}\) (8) and [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(CH\(_{2}\)CO\(_{2}\)Et)]\(^{-}\) (9).}, language = {en} } @article{FinzeReiss2012, author = {Finze, Maik and Reiss, Guido J.}, title = {Trimethyl­sulfonium 1-amino-6-fluoro-2,3,4,5,7,8,9,10,11,12-decaiodo-1-carba-closo-dodeca­borate}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-75397}, year = {2012}, abstract = {no abstract available}, subject = {Chemie}, language = {en} }