Manfred Scheer

Universität Regensburg, Ratisbon, Bavaria, Germany

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Publications (313)1339.62 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: While reacting the sterically demanding triphosphaferrocene [Cp*Fe(η5-P3C2Mes2)] (1) with Cu(I) halides, the sandwich complex undergoes an unprecedented fragmentation into decamethylferrocene, FeX2 (X = Cl, Br, I) and [P3C2Mes2]- units. Subsequently, these phospholyl ligands act as versatile, negatively charged building blocks for the formation of supramolecular aggregates representing the monomeric, dimeric and polymeric (1D and 2D) coordination compounds [(μ,η1:η2:η2-P3C2Mes2)(μ,η1:η3:η3-P3C2Mes2){Cu7(CH3CN)7(μ4 X)(μ3 X)2(μ X)}{Cu2(μ X)2X}{Cu(CH3CN)(μ X)}]2 (2: X = Cl, 3: X = Br), [(μ,η1:η2:η3-P3C2Mes2)2{Cu(CH3CN)}6(μ2 Br)2(μ3 Br)2{Cu(CH3CN)2Br}2] (4a), [(μ,η1:η1:η2 P3C2Mes2)3(μ,η1:η2:η3 P3C2Mes2){Cu5(CH3CN)5(μ Br)}{Cu(CH3CN)2CuBr2}2 {Cu(CH3CN)2}]n+[CuBr2]n- (5), [(μ,η1:η2:η2 P3C2Mes2){Cu(CH3CN)(μ I)}4{Cu(CH3CN)3}] (6), [(μ,η1:η2:η2-P3C2Mes2)Cu7(CH3CN)4(μ4 I)2(μ3 I)2(μ I)2]x (7), [(μ,η1:η3:η3 P3C2Mes2){Cu(CH3CN)3}2{Cu(μ I)}6] (8) and [Cp*Fe(CH3CN)3]n+[(μ,η1:η3:η3 P3C2Mes2)2{Cu(CH3CN)2}{Cu(μ I)}6]n- (9) with rather non-typical structural motifs within the large varieties of the copper halide chemistry. Beside the X-ray structural analyses the obtained assemblies were also characterized in solution in which they undergo fragmentation and re-aggregation processes.
    Dalton Transactions 02/2015; · 4.10 Impact Factor
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    ABSTRACT: By the reaction of [NacnacCuCH3 CN] with white phosphorus (P4 ) and yellow arsenic (As4 ), the stabilization and enclosure of the intact E4 tetrahedra are realized and the disubstituted complexes [(NacnacCu)2 (μ,η(2:2) -E4 )] (1 a: E=P, 1 b: E=As) are formed. The mono-substituted complex [NacnacCu(η(2) -P4 )] (2), was detected by the exchange reaction of 1 a with P4 and was only isolated using low-temperature work-up. All products were comprehensively spectroscopically and crystallographically characterized. The bonding situation in the products as intact E4 units (E=P, As) was confirmed by theory and was experimentally proven by the pyridine promoted release of the bridging E4 tetrahedra in 1. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Angewandte Chemie International Edition in English 02/2015; · 13.45 Impact Factor
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    ABSTRACT: Die Reaktion der Pentelidenkomplexe [Cp*E{W(CO)5}2] (E=P (1 a), As (1 b); Cp*=C5Me5) mit Carbodiimiden führt zu den neuen viergliedrigen Heterocyclen des Typs [Cp*C(NR)2E{W(CO)5}2] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). Die Reaktion des Phosphinidenkomplexes 1 a mit Alkylaziden ergibt die Triazaphosphetderivate [Cp*P{W(CO)5}N(R)NN{W(CO)5}] (R=Hex, Cy; 4). Diese beispiellosen viergliedrigen Triazaphosphetkomplexe können als stabilisierte Intermediate der Staudinger-Reaktion betrachtet werden, die bisher noch nicht isoliert werden konnten. Alle erhaltenen Produkte wurden durch NMR- und IR-Spektroskopie, Massenspektrometrie und durch Röntgenstrukturanalyse an Einkristallen charakterisiert.
    Angewandte Chemie 01/2015; 127(9).
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    ABSTRACT: The reaction of the phosphinidene and arsinidene complexes [Cp*E{W(CO)5}2] (E=P (1 a), As (1 b); Cp*=C5Me5) with carbodiimides leads to the new four-membered heterocycles of the type [Cp*C(NR)2E{W(CO)5}2] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). The reaction of phosphinidene complex 1 a with alkyl azides yields the triazaphosphete derivatives [Cp*P{W(CO)5}N(R)NN{W(CO)5}] (R=Hex, Cy) (4). These unprecedented N3P four-membered triazaphosphete complexes can be regarded as stabilized intermediates of the Staudinger reaction, which have not been previously isolated. All of the isolated products were characterized by NMR, IR spectroscopy, mass spectrometry, and by single-crystal X-ray diffraction analysis.
    Angewandte Chemie International Edition 01/2015; · 11.34 Impact Factor
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    ABSTRACT: A simple and straightforward synthesis of a new linear trinuclear CuI cluster with polyphosphine ligands is presented. The reaction of this pre-organized Cu3 precursor with En ligand complexes (E = P, As; n = 2, 5) affords discrete complexes exhibiting end-on η1-coordination of the E2 ligands of one-dimensional coordination polymers featuring σ-1,3-bridging E5 rings, respectively.
    Chemical Communications 01/2015; 51(14). · 6.38 Impact Factor
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    ABSTRACT: The reaction of [{η5-Cp‘‘‘Co}2{µ,η4:4-toluene}] with yellow arsenic yields the arsenic-rich Asn ligand complexes [{Cp‘‘‘Co(µ,η2:2-As2)}2] (1), [(Cp‘‘‘Co)4(µ4,η4:4:2:2:1:1-As10)] (2) and [(Cp‘‘‘Co)3(µ3,η4:4:2:1-As12)] (3), which were comprehensively characterized. The molecular structure of 1 show a triple-decker complex with two As2 units forming the middle-deck; compound 2 contains an all-arsenic As10 analogue of dihydrofulvalene in the molecular structure. The As12 ligand in 3 represents the largest Asn ligand complex reported so far.
    Chemical Science 11/2014; · 8.60 Impact Factor
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    ABSTRACT: P-H functional transition-metal complexes were synthesized without using hazardous PH3 gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)6-x (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P2(SiMe3)4 and subsequent methanolysis to give the bridging complexes [(CO)xM(μ-PH2)]2 (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)4M(μ-PH2)]2 (M = Cr (2a), M = W (2b)) with P(SiMe3)3 was applied followed by methanolysis to synthesize the PH2 bridging transition-metal binuclear complexes with terminal PH3 groups. The products [(CO)4M(μ-PH2)2M(CO)3(PH3)] (M = Cr (3a), M = W (3b)) and [(CO)4W(μ-PH2)2W(CO)2(PH3)2] (4b) were isolated in moderate yield. Another synthetic approach to this type of compounds is the direct photolysis of the complexes [(CO)3M(PH3)3] (M = Cr (5a), M = W (5b)). The products were comprehensively characterized by (31)P NMR and IR spectroscopy as well as by X-ray structural analysis. Additionally, the relevancy of 2a as single source precursor for the synthesis of stoichiometry-controlled CrP nanoparticles has been demonstrated.
    Inorganic Chemistry 10/2014; · 4.79 Impact Factor
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    ABSTRACT: The reaction of [CpBnFe(η5-P5)] (1) (CpBn=η5-C5(CH2Ph)5) with CuI selectively yields a novel spherical supramolecule (CH2Cl2)3.4@[(CpBnFeP5)12{CuI}54(MeCN)1.46] (2) showing a linkage of the scaffold atoms which is beyond the Fullerene topology. Its extended CuI framework reveals an outer diameter of 3.7 nm—a size that has not been reached before using five-fold symmetric building blocks. Furthermore, 2 shows a remarkable solubility in CH2Cl2, and NMR spectroscopy reveals that the scaffold of the supramolecule remains intact in solution. In addition, a novel 2D polymer [{CpBnFe(η5-P5)}2{Cu6(μ-I)2(μ3-I)4}]n (3) with an uncommon structural motif was isolated. Its formation can be avoided by using a large excess of CuI in the reaction with 1.
    Angewandte Chemie International Edition 10/2014; · 11.34 Impact Factor
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    ABSTRACT: Die Reaktion von [CpBnFe(η5-P5)] (1) (CpBn=η5-C5(CH2Ph)5) mit CuI ergibt selektiv das neue sphärische Supramolekül (CH2Cl2)3.4@[(CpBnFeP5)12{CuI}54(MeCN)1.46] (2), welches eine Verknüpfung von Gerüstatomen jenseits der Fulleren-Topologie zeigt. Sein ausgedehntes CuI-Gerüst weist einen Außendurchmesser von 3.7 nm auf – eine Größe, die bisher nicht erreicht wurde, wenn fünffach symmetrische Bausteine hierfür verwendet wurden. Weiterhin weist 2 eine bemerkenswerte Löslichkeit in CH2Cl2 auf, und NMR-Experimente belegen, dass das Gerüst des Supramoleküls in Lösung intakt bleibt. Zusätzlich wurde das neue 2D-Polymer [{CpBnFe(η5-P5)}2{Cu6(μ-I)2(μ3-I)4}]n (3) mit einem ungewöhnlichen Strukturmotiv isoliert. Seine Bildung kann durch einen großen Überschuss an CuI in der Reaktion mit 1 verhindert werden.
    Angewandte Chemie 10/2014;
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    ABSTRACT: The selective formation of the dinuclear butterfly complexes [{Cp′′′Fe(CO)2}2(μ,η1:1-E4)] (E=P (1 a), As (1 b)) and [{Cp*Cr(CO)3}2(μ,η1:1-E4)] (E=P (2 a), As (2 b)) as new representatives of this rare class of compounds was found by reaction of E4 with the corresponding dimeric carbonyl complexes. Complexes 1 b and 2 b are the first As4 butterfly compounds with a bridging coordination mode. Moreover, first studies regarding the reactivity of 1 b and 2 b are presented, revealing the formation of the unprecedented As8 cuneane complexes [{Cp′′′Fe(CO)2}2{Cp′′′Fe(CO)}2(μ4,η1:1:2:2-As8)] (3 b) and [{Cp*Cr(CO)3}4(μ4,η1:1:1:1-As8)] (4). The compounds are fully characterized by NMR and IR spectroscopy as well as by X-ray structure analysis. In addition, DFT calculations give insight into the transformation pathway from the E4 butterfly to the corresponding cuneane structural motif.
    Angewandte Chemie International Edition 08/2014; 53(34). · 11.34 Impact Factor
  • Sebastian Heinl, Gábor Balázs, Manfred Scheer
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    ABSTRACT: A new synthesis of [CpBIGFe(CO)2]23 (CpBIG = C5(4-nBuC6H4)5) was developed starting from CpBIGNa and FeCl2 in the presence of CO. Reaction of this product with P4 leads to the two new Pn ligand complexes [CpBIGFe(η5-P5)] 1b and [(CpBIGFe)2(μ,η4:4-P4)] (4) containing the highly sterically demanding CpBIG ligand. Depending on the solvent, different ratios of 1b:4 are obtained. The products 1b, 3, and 4 were characterized by spectroscopic methods as well as by X-ray diffraction.
    Phosphorus Sulfur and Silicon and the Related Elements 08/2014; 189. · 0.83 Impact Factor
  • Manfred Scheer, Sebastian Heinl
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    ABSTRACT: The bulky dimeric iron complex, [CpBIGFe(CO)2]2, readily activates elemental chalcogens (S8, Sered and α-Te) under mild conditions at room temperature. Six compounds containing (Q2)2- ligands (Q = S, Se) and a Te2- ligand, respectively, were isolated and completely characterized, including by X-ray diffraction techniques.
    Dalton Transactions 07/2014; · 4.10 Impact Factor
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    ABSTRACT: Durch die Reaktion von [Cp*Fe(η5-P5)] (1; Cp* = η5-C5Me5) mit verschiedenen Nucleophilen werden beispiellose funktionalisierte Produkte mit einem η4-P5-Ring erhalten. Mit LiCH2SiMe3 und LiNMe2 werden die Monoanionen [Cp*Fe(η4-P5CH2SiMe3)]− bzw. [Cp*Fe(η4-P5NMe2)]− gebildet. Die Reaktion von 1 mit NaNH2 führt zur Bildung des Trianions [{Cp*Fe(η4-P5)}2N]3−, während die Reaktion mit LiPH2 [Cp*Fe(η4-P5PH2)]− als das Hauptprodukt ergibt, mit {[Cp*Fe(η4-P5)]2PH}2− als Nebenprodukt. Die berechneten Energieprofile der Reaktionen liefern eine Erklärung für die Bildung der unterschiedlichen Produkte.
    Angewandte Chemie 07/2014; 126(29).
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    ABSTRACT: Eine neue einstufige und selektive Synthese für den ersten Schritt der Aktivierung von weißem Phosphor wurde unter Verwendung organischer Radikale entwickelt. Die Reaktion von NaCpR mit P4 in Gegenwart von CuX oder FeBr3 führt zur direkten Bildung der organisch substituierten P4-Butterfly-Verbindungen CpR2P4 (CpR: CpBIG=C5(4-nBuC6H4)5 (1 a), Cp′′′=C5H2tBu3 (1 b), Cp*=C5Me5 (1 c) und Cp4iPr=C5HiPr4 (1 d)). Die Reaktion verläuft über die Aktivierung von P4 mittels CpR-Radikalen, die durch Übergangsmetallen erzeugt wurden. Die neu gebildeten organischen P4-Derivate wurden durch NMR-Spektroskopie und Röntgenstrukturanalyse umfangreich charakterisiert.
    Angewandte Chemie 07/2014; 126(29).
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    ABSTRACT: Die selektive Bildung der zweikernigen Butterflykomplexe [{Cp′′′Fe(CO)2}2(μ,η1:1-E4)] (E=P (1 a), As (1 b)) und [{Cp*Cr(CO)3}2(μ,η1:1-E4)] (E=P (2 a), As (2 b)) als neue Vertreter dieser seltenen Verbindungsklasse wurde durch die Reaktion von E4 mit den entsprechenden dimeren Carbonylkomplexen gefunden. Die Komplexe 1 a und 2 b repräsentieren die ersten As4-Butterflyverbindungen in einer verbrückenden Koordinationsform. Überdies werden erste Studien zur Reaktivität von 1 und 2 b präsentiert, die die Bildung der präzedenzlosen As8-Cuneankomplexe [{Cp′′′Fe(CO)2}2{Cp′′′Fe(CO)}2(μ4,η1:1:2:2-As8)] (3 b) und [{Cp*Cr(CO)3}4(μ4,η1:1:1:1-As8)] (4) zeigen. Die Verbindungen sind vollständig durch NMR- und IR-Spektroskopie sowie durch Röntgenstrukturanalyse charakterisiert. Zusätzlich geben DFT-Rechnungen Einsicht in den Umwandlungsweg von der E4-Butterflystruktur zum entsprechenden Strukturmotiv des Cuneans.
    Angewandte Chemie 07/2014;
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    ABSTRACT: Unprecedented functionalized products with an η(4) -P5 ring are obtained by the reaction of [Cp*Fe(η(5) -P5 )] (1; Cp*=η(5) -C5 Me5 ) with different nucleophiles. With LiCH2 SiMe3 and LiNMe2 , the monoanionic products [Cp*Fe(η(4) -P5 CH2 SiMe3 )](-) and [Cp*Fe(η(4) -P5 NMe2 )](-) , respectively, are formed. The reaction of 1 with NaNH2 leads to the formation of the trianionic compound [{Cp*Fe(η(4) -P5 )}2 N](3-) , whereas the reaction with LiPH2 yields [Cp*Fe(η(4) -P5 PH2 )](-) as the main product, with {[Cp*Fe(η(4) -P5 )]2 PH}(2-) as a byproduct. The calculated energy profile of the reactions provides a rationale for the formation of the different products.
    Angewandte Chemie International Edition in English 06/2014; 53(29). · 13.45 Impact Factor
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    ABSTRACT: A new and selective one-step synthesis was developed for the first activation stage of white phosphorus by organic radicals. The reactions of NaCp(R) with P4 in the presence of CuX or FeBr3 leads to the clean formation of organic substituted P4 butterfly compounds Cp(R) 2 P4 (Cp(R) : Cp(BIG) =C5 (4-nBuC6 H4 )5 (1 a), Cp'''=C5 H2 tBu3 (1 b), Cp*=C5 Me5 (1 c) und Cp(4iPr) =C5 HiPr4 (1 d)). The reaction proceeds via the activation of P4 by Cp(R) radicals mediated by transition metals. The newly formed organic derivatives of P4 have been comprehensively characterized by NMR spectroscopy and X-ray crystallography.
    Angewandte Chemie International Edition in English 05/2014; · 13.45 Impact Factor
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    ABSTRACT: Invited for the cover of this issue is the group of Manfred Scheer at the University of Regensburg. The cover image shows organometallic and inorganic building blocks being combined to form unprecedented new species.
    Berichte der deutschen chemischen Gesellschaft 04/2014; 2014(10). · 2.97 Impact Factor
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    ABSTRACT: By using [(Cp″′Co)2tol] (Cp″′ = η5-C5H2tBu3, tol = toluene), a new synthesis of the 1,3-diphosphete complexes [Cp″′Co(η4-P2C2tBu2)] (1a) and [Cp″′Co(η4-P2C2iPr2)] (1b) was found, and their reactions with the Lewis acids W(CO)4 and CuI halides were investigated. The reaction of 1b with W(CO)4(nbd) (nbd = norbornadiene) leads to the complex [(Cp″′Co)(μ,η4:1-{PCiPr}2)]2W(CO)4 (2) with the two diphosphete complexes 1b coordinated trans to a central W(CO)4 moiety. The reactions of 1a with CuI halides result in different products depending on the stoichiometry. In a 1:1 ratio, the dimeric compounds 3a–c [(Cp″′Co)(μ,η4:1-{PCtBu}2)Cu(μ-X)]2 (3a: X = Cl; 3b: X = Br, 3c: X = I) were isolated, whereas an excess of CuX gave the two-dimensional polymers [({Cp″′Co}{μ3,η4:1:1-(PCtBu)2})2(Cu{μ3-X})4]n (6a: X = Cl, 6b: X = Br, 6c: X = I). From the reaction of 1a and 1b with CuBr and CuI in a 1:2 or 2:3 ratio, the one-dimensional polymers [({Cp″′Co}{μ3,η4:1:1-(PCR)2})({Cp″′Co}{μ,η4:1-(PCR)2})(Cu{μ3-X})4]n (4a: X = Br, R = iPr, 4b: X = I, R = iPr, 4c: X = I, R = tBu) are formed. From the reaction of 1a with CuI, a second product, [({Cp″′Co}{μ3,η4:1:1-(PCtBu)2})(Cu{μ3-I})4(MeCN)2]n (5), was isolated by using CH3CN for crystallization. The products were comprehensively characterized by spectroscopic methods, X-ray crystallography, and 31P magic angle spinning (MAS) NMR spectroscopy.
    Berichte der deutschen chemischen Gesellschaft 04/2014; 2014(10). · 2.97 Impact Factor
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    ABSTRACT: Chromium(II) chloride reacts with lithium pentamethylcyclopentadienide (LiCp*, Cp* = C5Me5) and LiE(SiMe3)2 (E = P or As) to give the heterocubane chromium phosphide [(η5-Cp*Cr)(μ3-P)]4 (1) or the chromium arsenide cage [(η5-Cp*Cr)3(μ3-As)2] (2), respectively. The crystal and molecular structures of both compounds have been determined by X-ray crystallography. The reactions represent unusual oxidative additions of pnictogen atoms to chromium(II), which in the case of 1 results in the formation of the unusual chromium(IV) formal oxidation state, and in the case of 2 provides access to chromium(III). Compound 1 is also a rare example of a transition metal μ3-phosphide-ligated cubane. Magnetic susceptibility and magnetization measurements, with support from DFT calculations, indicate S = 2 and S = 9/2 ground states for 1 and 2, respectively, which can be rationalized by considering the electronic structure in terms of chromium-chromium bonding.
    Chemical Science 03/2014; · 8.60 Impact Factor

Publication Stats

2k Citations
1,339.62 Total Impact Points


  • 2005–2015
    • Universität Regensburg
      • Institute of Inorganic Chemistry
      Ratisbon, Bavaria, Germany
  • 2011–2013
    • Saint Petersburg State University
      • Faculty of Chemistry
      Sankt-Peterburg, St.-Petersburg, Russia
    • The University of Manchester
      • School of Chemistry
      Manchester, ENG, United Kingdom
    • Novosibirsk State University
      Novo-Nikolaevsk, Novosibirsk, Russia
  • 1997–2013
    • Karlsruhe Institute of Technology
      • Institut für Anorganische Chemie
      Eggenstein-Leopoldshafen, Baden-Wuerttemberg, Germany
  • 2010
    • Russian Academy of Sciences
      • Kurnakov Institute of General and Inorganic Chemistry
      Moskva, Moscow, Russia
  • 2008
    • The Ohio State University
      • Department of Chemistry and Biochemistry
      Columbus, OH, United States
  • 2007–2008
    • Nanjing University
      • • State Key Laboratory of Coordination Chemistry
      • • Department of Chemical Engineering
      Nanjing, Jiangsu Sheng, China
  • 1993
    • Indiana University Bloomington
      Bloomington, Indiana, United States
  • 1991–1993
    • Universitätsklinikum Halle (Saale)
      Halle-on-the-Saale, Saxony-Anhalt, Germany
  • 1988–1993
    • Martin Luther University of Halle-Wittenberg
      • • Division of Inorganic Chemistry
      • • Institute of Chemistry
      Halle-on-the-Saale, Saxony-Anhalt, Germany
  • 1991–1992
    • Technische Universität Braunschweig
      • Institute of Inorganic and Analytical Chemistry
      Braunschweig, Lower Saxony, Germany