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  • 1
    Electronic Resource
    Electronic Resource
    1,6-Heptadien-Nickel(0)-Komplexe: rac/meso-(μ-η2,η2-C7{Ni( η2,η2-C7H12)}2 und L-Ni(η2,η2-C7H12) (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2667-2675 
    Details
    ISSN: 0009-2940
    Keywords: Alkene ligands ; 1,6-Dienes ; Nickel complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,6-Heptadiene Nickel(0) Complexes:rac/meso-(μ-η2,η2-C7{Ni(η 2,η2-C7H12)}2 und L-Ni(η2,η2-C7H12)Ni(CDT) dissolves in 1,6-heptadiene with displacement of the CDT to yield the dinuclear homoleptic product rac/meso-(μ- η2,η2-C7H12){Ni(η2, η2-C7H12)}2 (1) as a mixture of stereoisomers, in which the nickel atoms are trigonal-planar coordinated by a chelating 1,6-diene ligand and one C=C bond of a bridging diene ligand. The stereoisomers differ in the coordination mode of the bridging diene ligand.-The bridging diene ligand in 1 can be displaced by various donor/acceptor molecules. In pentane, 1 reacts with ethene to yield a solution of mononuclear (C2H4)Ni(η2,η2-C7H12) (2). With alkynes unstable complexes are formed of which the anticipated ethyne derivative (C2H2)Ni(η2,η2-C7H12) (3) decomposes explosively at - 100°C. With isocyanides, methylenephosphoranes, methyllithium, amines, pyridines, phosphanes, and phosphites (i.e. C, N, P donors) crystalline complexes of type L-Ni(η2.η2 C7H12) have been obtained, of which the derivatives with L=tBuN = C 4, Me3PCH2 5, LiCH3 6, C7H13N7, C5H5N 8, Me3P 9, iPr3P 10, Ph3P 11, (PhO)3P 12 are characterized here. For 11 the crystal structure has been determined.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19911241206
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  • 2
    Electronic Resource
    Electronic Resource
    Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe, IV. Synthese, Struktur und Reaktivität von Zweikernkomplexen des Rhodiums und Iridiums in der Oxidationsstufe +I und +III mit dem Bis(cyclopentadienyl)methan-Dianion als Brückenliganden (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 337-346 
    Details
    ISSN: 0009-2940
    Keywords: Dinuclear rhodium and iridium complexes ; Bis(cyclopentadienyl)methane dianion as bridging ligand ; Substitution and bridge-splitting reactions ; Rhodium complexes ; Iridium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(cyclopentadienyl)methane-Bridged Dinuclear Complexes, IV[1].  -  Synthesis, Structure, and Reactivity of Dinuclear Rhodium and Iridium Complexes in the Oxidation State +I and +III with the Bis(cyclopentadienyl)methane Dianion as Bridging LigandThe rhodium compounds [CH2(C5H4)2][Rh(L)(C2H4)]2 (2, 4) were prepared from [RhCl(L)(C2H4)]2 (1, 3) and CH2(C5H4)2Li2 in 92 and 73% yield, respectively. The reaction of 4 with Cl2, Br2, and I2 led to the almost quantitative formation of the dihalogeno derivatives [CH2(C5H4)2][RhX2(PiPr3)]2 (6-8), which on treatment with excess NaBH4 and methanol gave the dihydride [CH2(C5H4)2][RhH2(PiPr3)]2 (10). From [RhCl(C8H14)2]2 (12), PiPr3, and CH2(C5H5)2 the chloro(hydrido)rhodium complex [CH2(C5H4)2][RhH(Cl)(PiPr3)]2 (13) was obtained. Protonation of 10 with CF3CO2H in the presence of NH4PF6 gave the PF6 salt of the hydrido-bridged cation {[CH2(C5H4)2]-[RhH(PiPr3)]2(μ-H)}+ (14) of which the crystal structure was determined. In solution, fluxional behavior of the cation was observed. The dimethyl compound [CH2(C5H4)2][Rh(CH3)2-(PiPr3)]2 (17), prepared from 6, 7, or 8 and LiCH3 or CH3MgI in 80% yield, reacted with CF3CO2H at  -  78° C to give the tri-fluoroacetato derivative 18; this on treatment with P(OMe)3 and dmpe formed the dicationic complexes 19 and 20, respectively. The dinuclear iridium compounds [CH2(C5H4)2]-[Ir(olefin)2]2 (26, 27) and [CH2(C5H4)2][Ir(C8H12)]2 (28) were prepared from [IrCl(L)2]2 (23-25) and CH2(C5H4)2Li2 and used for the synthesis of {[CH2(C5H4)2][IrX2]2}n (29, 30). Compounds 29 and 30 served as starting materials for the preparation of the dinuclear derivatives [CH2(C5H4)2][IrX2(L)]2 (31-34) and {[CH2(C5H4)2][IrBr2]2(μ-dipy)} (35) and finally also for the dihydrido complex [CH2(C5H4)2][IrH2(PiPr3)]2 (36).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250210
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  • 3
    Electronic Resource
    Electronic Resource
    Charge-Transfer-Komplexe von Metalldithiolenen, XIII. cis-trans-Photoisomerisierbare Viologene als redoxaktive Akzeptoren  - Synthese und elektrische LeitfähigkeitHerrn Prof. Dr. C. Krüger zum 60. Geburtstag gewidmet. (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 287-294 
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    ISSN: 0009-2940
    Keywords: Metal dithiolenes ; Dipyridinioethylene dihalides ; Charge-Transfer complexes ; Electrical conductivity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Charge-Transfer Complexes of Metal Dithiolenes, XIII[1]. - cis-trans-Photoisomerisable Viologens as Redoxactive Acceptors  -  Synthesis and Electrical ConductivityIon Pair Charge-Transfer (IPCT) complexes of the type [A2+[ML2]2-} (1a-f to 4a-f) are synthesized from dianionic metal dithiolenes [M = Ni, Zn, L = cis-1,2-dicyano-1,2-ethene-dithiolate (mnt2-), 2-thioxo-1,3-dithiol-4,5-dithiolate (dmit2-)] and dicationic viologens [A2+ = 4,4′-(1,2-ethenediyl)bis(1-alkylpyridinium)]. The acceptors can exist as cis/trans isomers and may have coordinating properties in the case of 1-cyanoalkyl groups. The IPCT bands are in the range of 500 to 1200 nm and their energy follows the Hush-Marcus relation. For the nickel complexes the reorganization energy amounts to 73, for the zinc compounds to 115 kJ/mol. As shown by X-ray analysis of {A2+[Ni(mnt)2]2-} (2d), A2+ = trans-4,4′-(1,2-ethenediyl)-bis[1-(3-cyanopropyl)pyridinium], the structure consists of stacks of alternating donors and acceptors with a typical plane-to-plane distance of 350 pm. There is no interaction between the cyano group of the acceptor and the nickel atom of the donor. The electrical conductivities of the nickel compounds are in the range of 5 · 10-6 to 3 · 10-11 Ω-1 cm-1, and the corresponding activation energies vary from 0.24 to 0.61 eV. For the dmit complexes these values agree well with the free activation enthalpy of the electron transfer reaction A2+ + [ML2]2- → A+ + [ML2]- calculated from the Hush-Marcus model. This suggests that charge carrier generation occurs by electron transfer. When a trans acceptor is replaced by its cis isomer in [A2+[NiL2]2-}, conductivity changes from 5 · 10-7 to 5 · 10-6 Ω-1 cm-1 and the activation energy from 0.43 to 0.24 eV, when L - dmit2- but stays at about 1 · 10-8 Ω-1 cm-1 for L = mnt2-.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270203
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  • 4
    Electronic Resource
    Electronic Resource
    Das Chromogen III der Morgan-Elson-Reaktion (1957)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 90 (1957), S. 264-277 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus N-Acetyl-D-glucosamin läßt sich kristallisiertes Chromogen III in einer Ausbeute von 40% d. Th. gewinnen. Dieselbe Verbindung wird, wie es die Theorie verlangt, auch aus N-Acetyl-D-galaktosamin erhalten. Es handelt sich um D(+)-5-Dihydroxyäthyi-3-acetamino-furan (I). Diese Konstitution wird gesichert durch eine Synthese der DL-Verbindung, die von Äpfelsäure (4 kg) ausgeht und 17 Reaktionsschritte erforderlich gemacht hat. Das synthet. Racemat stimmt mit dem Chromogen III, das wir aus einem künstlichen Gemisch von 50% D- und 50% L-Acetylglucosamin erhalten haben, genau überein. Aus dem Chromogen III wurde durch katalytische Hydrierung, Abspaltung der Acetylgruppe und Umsetzung mit Methyljodid ein quartäres Ammoniumsalz erhalten, das sich vom Muscarin durch Austausch der end-ständigen CH3-Gruppe gegen CH2OH unterscheidet; die sterischen Verhältnisse an 2 C-Atomen sind noch unbekannt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19570900222
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  • 5
    Electronic Resource
    Electronic Resource
    Di-μ-hydrido-bis[1,3-propanbis(dicyclohexylphosphin)]dinickel(Ni—Ni)  -  Der Bindungszustand in einem Dreizentren-Wasserstoff-überbrückten Ni—Ni-System (1977)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 3900-3909 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Di-p-hydrido-bis[1,3-propanbis(dicyclohexylphosphin)]dinickel(Ni—Ni) - Der Bindungszustand in einem Dreizentren-Wasserstoff-überbrückten Ni—Ni-SystemDie Kristallstruktur der Titelverbindung [(C6H11)2PCH2CH2CH2P(C6H11)2NiH]2 (1) wurde aus 4051 Reflexen abgeleitet und zu einem R-Wert von 0.044 verfeinert. Lageparameter aller Wasserstoffatome konnten einer Differenz-Fourier-Synthese entnommen werden. Die Struktur der diamagnetischen Verbindung setzt sich aus zwei P2Ni-Untereinheiten zusammen, welche zweifach mit Wasserstoffatomen (Ni—H 1.6 Å) überbrückt sind. Hierdurch ergibt sich ein bindender Ni—Ni-Abstand von 2.441(1) Å. Im Kristallgitter bilden die Ebenen durch die P2Ni-Untereinheiten einen Interplanarwinkel von 63.3°. Theoretische Betrachtungen sagen für das freie Molekül eine quadratisch planare Anordnung voraus, doch ergibt sich für die Drehbewegung zur beobachteten Geometrie nur eine flache Potentialenergiefläche. Die gefundene Verdrillung resultiert aus starken intramolekularen Abstoßungskräften zwischen den Cyclohexylgruppen der zwei P2Ni-Einheiten.
    Notes: The crystal structure of the title compound, [(C6H11)2PCH2CH2CH2P(C6H11)2NiH]2 (1), has been determined from 4051 reflections and refined to a final R-value of 0.044. The positions of the hydrogen atoms (bridging and non-bridging) have been determined from a difference Fourier synthesis. The molecular structure of the diamagnetic compound consists of subunits doubly-bridged by hydrogen atoms. The Ni—Ni and average Ni—H distances are 2.441 and 1.6 Å, respectively. In the solid state the two planes of the P2Ni units form a dihedral angle of 63.3°. Theoretical considerations predict a square-planar structure for the idealized molecule with a soft potential energy surface for a twisting motion towards the observed geometry. The observed twist is the result of severe intramolecular repulsions between the cyclohexyl groups of the two P2Ni units.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19771101221
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  • 6
    Electronic Resource
    Electronic Resource
    Difluorophosphate von Zinn(IV) und Antimon(V) (1978)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 438 (1978), S. 169-175 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Difluorophosphates of Tin (IV) and Antimony(V)Preparation and properties of SnCl2(PO2F2)2 (l), Cl4Sb(O2PF2) (2) and F4Sb(O2PF2) (3) are described. According to their vibrational spectra the structures are assumed. 31P-nmr spectra of 2 and 3 are given. 1 is characterised additional by its 119Sn-Mössbauer spectrum.
    Notes: Darstellung und Eigenschaften von SnCl2(PO2F2)2 (1), SbCl4(PO2F2) (2) und F4Sb(O2PF2) (3) werden beschrieben. Aus den Schwingungsspektren werden Strukturvorschläge abgeleitet. 31P-KMR-Spektren werden für 2 und 3 mitgeteilt, 1 wird zusätzlich durch das 119Sn-Mößbauer-Spektrum charakterisiert.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19784380118
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  • 7
    Electronic Resource
    Electronic Resource
    Elementorganische Amin/Imin-Verbindungen, XXII. ΛLD3-Phosphazen-Komplexe des nullwertigen Platins (1982)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 414-426 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Element-Organic Amine/Imine Compounds, XXII. λ3-Phosphazene Complexes of Zerovalent PlatinumThe reaction of Pt(COD)2 (COD = 1,5-cyclooctadiene) with the λ3-phosphazene RR'N—P=NR, R = (CH3)3C, R' = (CH3)3Si(1), gives the platinum(0) complex PtL3 (2) (L = λ3-phosphazene 1) whose structure has been elucidated by an X-ray analysis. 2 is used for the synthesis of the platinum(0) compounds PtL2L' (L' = R3M, M = P→b) (3) and PtLL2' (L' = R3P) (4).
    Notes: Die Umsetzung von Pt(COD)2 (COD = 1,5-Cyclooctadien) mit dem λ3-Phosphazen RR'N—P=NR, R = (CH3)3C, R' = (CH3)3Si(1), ergibt den Platin(0)-Komplex PtL3 (2) (L = λ3-Phosphazen 1), von dem eine Röntgenstrukturanalyse angefertigt wurde. Die Synthese der Platin(0)-Verbindungen PtL2L' (L' = R3M, M = P→b) (3) und PtLL2′ (L' = R3P) (4) erfolgte aus 2.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19821150203
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  • 8
    Electronic Resource
    Electronic Resource
    Organische Synthesen mit Übergangsmetallkomplexen, 8. Untersuchungen zur Synthese ungesättigter δ-Lactone durch Cyclocarbonylierung von Vinyloxiranen mit Übergangsmetall-Komplexen (1979)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3644-3671 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Syntheses by Means of Transition Metal Complexes, 8 - Synthesis of Unsaturated δ-L-Lactones from Vinyloxiranes and Carbon Monoxide via Transition Metal ComplexesThe transition metal-assisted carbonylation of vinyloxiranes to unsaturated δ-lactones has been verified and studied mechanistically by use of organometallic model reactions. The light induced complexation of vinyloxiranes 1 by Fe(CO)5 was shown to be a multistep reaction in which diastereomeric cis-resp. trans- ferralactones 2 are formed. Complexes of both types (2k, 2k′) were characterized crystallographically and studied chemically concerning their reactions with nucleophiles and electrophiles. Reaction with primary amines gives ferralactames 7 by migration of the allyl group and inversion at C-1 as well as C-4 indicating an attack of amine at the exo-position of C-4. On the other hand the reaction with HO⊖ leads to the formation of CO23⊝ and diene complexes 10 with inversion at C-1 only, indicating that the reaction has been initiated by attack of HO⊖ at a terminal carbonyl group. On electrophilic attack ferralactones form allyl cations (14, 16) by opening of the CO - O bond. Carbonylation of ferralactones with CO in aprotic solvents give good yields of unsaturated δ-lactones (12). In the case of isoprene epoxide it has been shown that homogeneous catalytic cyclocarbonylation of vinyloxiranes can be of synthetic use.
    Notes: Anhand metallorganischer Modellreaktionen wurde die Cyclocarbonylierung von Vinyloxiranen zu ungesättigten δ-Lactonen untersucht. Die photochemisch initiierte Komplexierung von Vinyloxiranen 1 (X = O) an Fe(CO)5 verläuft mehrstufig und führt zu diastereomeren cis- bzw. trans-Ferralactonen 2. Vertreter beider Verbindungstypen (2k, 2 k′) wurden kristallographisch charakterisiert und chemisch bezüglich ihres Verhaltens gegenüber Nucleophilen und Elektrophilen studiert. Mit primären Aminen bilden sich Ferralactame 7 unter Wanderung des Allylsystems sowie unter Konfigurationsumkehr an C-1 und C-4, was den exo-Angriff des Amins an C-4 des Allylsystems beweist. Bei Einwirkung von HO⊝ hingegen zerfallen Ferralactone zu CO23⊝ und Dien-komplexen 10, wobei lediglich an C-1 eine Konfigurationsumkehr beobachtet wird. In diesem Fall greift HO⊝ somit an einer terminalen Carbonylgruppe an. Elektrophile bewirken die Spaltung der CO-O-Bindung unter Bildung von Allyl-Kationen (14, 16). Die Carbonylierung von Ferralactonen führt in aprotischen Lösungsmitteln in guten Ausbeuten zu ungesättigten S-Lactonen (12). Am Isoprenepoxid wurde gezeigt, daß auch die homogenkatalytische Cyclocarbonylierung von Vinyloxiranen gute Ausbeuten an δ-Lactonen ergibt und dieses Verfahren für Synthesen von Interesse ist.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19791121114
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  • 9
    Electronic Resource
    Electronic Resource
    Organylkomplexe von (η5-Cyclopentadienyl)(triorganophosphan)eisen (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 1987-2002 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organyl Complexes of (η-Cyclopentadienyl)(triorganophosphane)ironA series of organyliron complexes of the type Cp(L)2Fe—R (Cp = C5H5, C5H4Me, C5Me5; L = PhnMe3-nP, n = 0-3) (R = Me, Et, Bu, Ph, CH2CH2Ph, CH=CH2) have been prepared either from the corresponding iron chlorides (1-7) and organomagnesium compounds or from Cp(COD)FeLi (8, 9), organic halide, and phosphane. The thermal stability of the ethyliron complexes 17-24 towards β-H elimination (to give the (η2-ethylene)iron hydrides 37-39 or the Cp(L)2FeH compounds 40-48) increases with the basicity of the phosphane ligand and decreases with increasing methyl-substitution of the Cp ligand. The vinyliron compounds 29-32, 54 and 55 react with ethylene with insertion into the vinyl-Fe bond to give the (η3-crotyl)iron complexes 56-61 as the result of isomerization. The (η1, η2-alkenyl)iron compounds Cp(Me3P)Fe-[CH2]3-CH=CH2(Cp=C5H5 (62), C5Me5 (63) and (C5Me5)(Me3P)Fe-o-C6H4CH2CH=CH2 (67) were isolated and are stable at 20°C.
    Notes: Es wurde eine Reihe von Organyleisen-Komplexen des Types Cp(L)2Fe—R (Cp = C5H5, C5H4Me, C5Me5; L = PhnMe3-nP, n = 0-3) (R = Me, Et, Bu, Ph, CH2CH2Ph, CH=CH2) teilweise über die entsprechenden Eisenchloride (1-7) und Organomagnesium-Verbindungen, zum anderen Teil aus Cp(COD)FeLi (8, 9), Organohalogenid und Phosphan dargestellt. Die thermische Stabilität der Ethyleisen-Komplexe 17-24 gegenüber ß-H-Eliminierung zu den (η2-Ethylen)eisenhydriden 37-39 bzw. den Verbindungen Cp(L)2FeH (40-48) nimmt mit der Basizität des Phosphanliganden zu, jedoch mit zunehmender Methylsubstitution am Cp-Liganden ab. Die Vinyleisenverbindugen 29-32, 54, 55 reagieren mit Ethylen unter Insertion in die Vinyl-Fe-Bindung. Nach Isomerisierung entstehen die (η3-Crotyl)eisen-Komplexe 56-61. Als bei 20°C stabile (η1, η2-Alkenyl)eisen-Verbindungen wurden Cp(Me3P)Fe-[CH2]3-CH =CH2(Cp=C5H5 (62), C5Me5 (63) und (c5Me5)(ME3P)Fe-oC6H4CH2=CH2 (67) isoliert.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19871201210
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  • 10
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    Electronic Resource
    Reduktion von (Cyclobutadien)(cyclopentadienyl)- und (1,5-Cyclooctadien)- (cyclopentadienyl)nickel-Kationen (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 227-237 
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    ISSN: 0009-2940
    Keywords: Nickel sandwich complex / Voltammetry, cyclic / Electrochemistry / Reductive dimerization / ESR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reduction of (Cyclobutadiene)(cyclopentadienyl)- and (1,5-Cyclooctadiene)(cyclopentadienyl)nickel CationsCyclic voltammetry of the four cationic Ni sandwich complexes [Ni(C5R5)(C4R4')]+ (2: R = H, R' = Ph; 3: R = H, R' = Me; 4; R = Me, R' = Ph; 5: R = R' = Me) shows reversible one-electron reductions for the phenyl derivatives 2 and 4 and a peak pattern characteristic of reductive dimerization/oxidative monomerization for the methyl derivatives 3 and 5. The product of the reduction of 3 was isolated and characterized analytically and by an X-ray structure determination as the dimer 6 of 3, linked through cyclobutenyl rings, the first example for a dimerization of an electron-rich sandwich complex at a substituted C atom. EPR spectra of the neutral complexes 2 and 4 are compared to those of (1,5-cyclooctadiene)(cyclopentadienyl)nickel (7) and are interpreted in terms of a substantial static Jahn-Teller distortion.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19901230202
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  • 11
    Online Resource
    Online Resource
    Resilient and Responsible Smart Cities : The Path to Future Resiliency (2023)
    Cham :Springer International Publishing :
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    Keywords: Environmental management. ; Urban policy. ; Geography. ; Landscape architecture. ; Architecture. ; Landscape ecology. ; Environmental Management. ; Urban Policy. ; Regional Geography. ; Landscape Architecture. ; Cities, Countries, Regions. ; Landscape Ecology.
    Description / Table of Contents: ARID - An Augmented Reality Mobile Application for Interior Design -- A Human-centred Technology Approach to Pedestrian Safety in Smart Cities -- Smart cities of ASEAN: ensuring cybersecurity in the context of the 5G networks development -- A Machine Learning Approach for Locating Businesses along Main Arteries in Inner Artries -- Sustainable cities: Password GREEN -- Game Theory applied to smart village -- THE YOUTH SMART CITY - Coproducing the Next Urban Vision with the Young -- A Study an Innovative Smart City System with Blockhain Technology: Provide Better Living Environment for Human -- Quantitative Evaluation Method For Retrofitting Suburbia Practice.
    Abstract: This book is a compilation of diverse, yet homogenic, research papers that discuss current advances in Earth Observation and Geospatial Information Technologies to tackle new horizons concerning the digitization and information management in smart cities’ infrastructures. The book also tackles the challenges faced by urban planners by the new mega-cities and proposes a series of solutions to resolve complex urban issues. It suggests enhancing the integration of disciplines, thus, bringing together architects, urban planners, civil engineers, landscape designers and computer scientists to address the problems that our cities are facing. This book is a culmination of selected research papers from IEREK’s fourth edition of the International Conference on Future Smart Cities (FSC) and the fourth edition of the International Conference on Resilient and Responsible Architecture and Urbanism (RRAU) held online in collaboration with the XMUM, Selangor, Malaysia (2021).
    Type of Medium: Online Resource
    Pages: XIV, 241 p. 159 illus., 140 illus. in color. , online resource.
    Edition: 3rd ed. 2023.
    ISBN: 9783031201820
    Series Statement: Advances in Science, Technology & Innovation, IEREK Interdisciplinary Series for Sustainable Development,
    URL: https://doi.org/10.1007/978-3-031-20182-0
    DOI: 10.1007/978-3-031-20182-0
    DDC: 333.7
    Language: English
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  • 12
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    Synthesis and Characterization of Copper, Nickel and Cobalt Complexes of N,N′-Dimethyl-2,11-diaza[3,3](2,6)pyridinophane (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 531-539 
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    ISSN: 0009-2940
    Keywords: 2,11-Diaza[3,3](2,6)pyridinophane ; N,N′-dimethyl- ; Tetraazamacrocyclic complexes ; cis-Octahedral coordination geometry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The properties of the tetraazamacrocyclic compound N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane (L-N4Me2) as a ligand for some selected metal chlorides have been examined. The crystal structure of the uncoordinated ligand reveals a syn chair-chair conformation. In solution, the ligand displays fluctional behavior. Reaction of L-N4Me2 with the chlorides of copper(II), nickel(II), and cobalt(II) affords the complexes [Cu(L-N4Me2)Cl2] · H2O (3), [Ni(L-N4Me2)(H2O)Cl]Cl · H2O (4), and [Co(L-N4Me2)Cl2] · 2 H2O (5) in which the ligand adopts a syn boat-boat conformation. The crystal structures of 4 and 5 are presented. Due to the small cavity of the 12-membered ring of the ligand, exclusively distorted cis-octahedral coordination geometries are found at the metal sites. A comparison of structural data of several complexes with this ligand shows that the extent of the distortions from ideal octahedral geometry is mainly determined by the M-Npy bond strength. The electronic as well as the solution properties of the described complexes have been investigated by electronic absorption spectroscopy. ESR spectroscopy, and electrochemical methods.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280602
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    Über das Kupfersuperoxyd (1907)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 54 (1907), S. 121-140 
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    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die einzige Methode, um Kupfersuperoxyd CuO2.H2O zu erhalten, besteht in der Oxydation von fein verteiltem Kupferoxydhydrat durch Wasserstoffsuperoxyd (15-30%) in neutraler Lösung, wobei die Temperatur nahe dem 0-Punkte sein soll. Im feuchten Zustande zerfällt das Kupfersuperoxyd rasch unter Abgabe von Sauerstoff und Wasser, trocken geht dieser Zerfall nur langsam vor sich. Durch die Einwirkung von Chlor und Brom in alkalischer Lösung wird nur Kupferoxyd erhalten und sind die gegenteiligen Angaben von Krüger und Vitali unrichtig. Auch Persulfate bewirken in alkalischer Lösung keine Oxydation in Cuprisalzen. Durch Natriumsuperoxyd entsteht zwar Kupfersuperoxyd, doch tritt infolge der alkalischen Flüssigkeit ein außerordentlich rascher Zerfall desselben ein. Schliefslich ist die Beobachtung von W. Schmid unrichtig, der durch Behandlung von Cuprisulfat mit Mangansuperoxyd Kupfersuperoxyd erhalten haben will.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19070540111
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  • 14
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    Untersuchungen zur Reaktivität von Metall-π-Komplexen, XXII. Sandwichartig gebaute (Pd-Pd)-Zweikernkomplexe mit brückenbildenden Cyclopentadienyl- und Allyl-Liganden (1977)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 1763-1775 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on the Reactivity of Metal π-Complexes, XXII. Sandwich-like Dinuclear (Pd-Pd)-Complexes with Bridging Cyclopentadienyl and Allyl LigandsThe reaction of C5H5Pd(2-RC3H4) (2-RC3H4 = 2-R-allyl) with tertiary phosphines or phosphites in the molar ratio of 1:1 produces in practically quantitative yields the dinuclear complexes (C5H5)(2-RC3H4)Pd2L2 (4-20) in which palladium has the oxidation state +1. The crystal structure analysis of 5 (R = CH3, L = P(C6H5)3) and 12 (R = CH3, L = P(OC6H4-o-CH3)3) shows that the cyclopentadienyl as well as the allyl ligand is bonded in a sandwich manner to the Pd-Pd unit. The Pd-Pd distance of 267.9 (in 5) or 268.9 pm (in 12) is suggestive of a metal-metal bond. It is not possible to determine whether the cyclopentadienyl ring in 4-20 exists as a pentahapto- or trihapto-bonded ligand on the basis of the 1H- and 13C n. m. r. data. The reactivity of the dinuclear complexes is in agreement with square planar coordination of the metal atoms.
    Notes: Bei den Reaktionen von C5H5Pd(2-RC3H4) (2-RC3H4 = 2-R-Allyl) mit tertiären Phosphinen oder Phosphiten im Molverhältnis 1:1 entstehen in praktisch quantitativer Ausbeute die Zweikernkomplexe (C5H5)(2-RC3H4)Pd2L2 (4-20), in denen Palladium in der Oxidationszahl +1 vorliegt. Wie die Kristallstrukturanalysen von 5 (R = CH3, L = P(C6H5)3) und 12 (R = CH3, L = P(OC6H4-o-CH3)3) zeigen, sind sowohl der Cyclopentadienyl- als auch der Allyl-Ligand sandwichartig an die Pd2-Einheit gebunden. Der Pd-Pd-Abstand von 267.9 (in 5) bzw. 268.9 pm (in 12) weist auf das Vorliegen einer Metall-Metall-Bindung hin. Aufgrund der 1H- und 13C-NMR-Daten ist nicht zu entscheiden, ob in 4-20 der Cyclopentadienylring als pentahapto-oder trihapto-gebundener Ligand vorliegt. Die Reaktivität der Zweikernkomplexe steht mit einer quadratisch-planaren Koordination der Metallatome in Einklang.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19771100522
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    Zur Lewis-Acidität von Nickel(0), I. Methyllithium-Komplexe von Nickel(0) (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 275-297 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Lewis Acidity of Nickel(0), I. Methyllithium Complexes of Nickel(0)The synthesis and properties of the methyllithium complexes of nickel(0) of the type (n-Donor)m-(LiCH3)Ni0(π-Ligand)n (1a-c, 16a-c, 20a-c) [n-Donor = chelating amine or THF; π-Ligand = CDT, ethene, or CO] are described. The structure of (PMDTA)(LiCH3)Ni(C2H4)2 (1b) has been determined by X-ray crystallography.  -  In these ate complexes, a carbanionic methyl group is σ-bonded to a nickel atom, the acceptor strength of which depend on the π-ligands. The chemical and spectroscopic properties indicate that the Ni—CH3 bond in the carbonyl complex is largely covalent whereas in the CDT and ethene compounds it is more polar. The CDT complex is thermolabile in solution. The findings are in agreement with the following series of increasing acceptor strength: Ni(CDT) 〈 Ni(C2H4)2 〈 Ni(CO)3.
    Notes: Es wird über die Synthese und Eigenschaften der Methyllithium-Komplexe von Nickel(0) (n-Donor)m(LiCH3)Ni0(π-Ligand)n Wir bezeichnen mitπ-Liganden solche Liganden, die als π-Akzeptoren mit einem Übergangsmetallatom dπ—pπ—oder dπ—dπ-Rückbindungen auszubilden vermögen (Alkene, CO, auch Phosphane);n-Donoren solche Liganden, die als „harte Basen“ (Ether, Amine) über ihre freien Elektronenpaare vornehmlich Hauptgruppenmetall-Ionen, d.h. „harte Säuren“ komplexieren;σ-Donoren solche Liganden, die  -  ohne über Akzeptororbitale zu verfügen  -  entweder polare Bindungen enthalten und Mehrzentrenbindungen eingehen können (Metallalkyle und -hydride) oder ein freies Elektronenpaar bereitstellen (Carbanionen, Phosphorane, Hydrid-Ion), wobei σ-Bindungen zu einem niederwertigen Übergangsmetallatom ausgebildet werden. (1a-c, 16a-c, 20a-c) mit Chelataminen oder THF als n-Donoren und CDTAbkürzungen: CDT = trans,trans,trans-l,5,9-Cyclooctadien; COT = Cyclooctatetraen; PMDTA = Pentamethyldiethylentriamin; TMEDA = Tetramethylethylendiamin; MA+A = Alkalimetall- bzw. quartäres Ammonium-Kation., Ethen oder CO als π-Liganden berichtet. Die Struktur von (PMDTA)(LiCH3)Ni(C2H4)2 (1b) wurde röntgenographisch bestimmt.  -  In diesen at-Komplexen ist eine carbanionische Methylgruppe über eine σ-Bindung an ein Nickelatom gebunden, dessen Akzeptorstärke von den π-Liganden abhängt. Chemische und spektroskopische Eigenschaften der Komplexe lassen für CDT oder Ethen als π-Liganden auf vergleichsweise polare, für den CDT-Komplex in Lösung dazu thermolabile Ni—CH3-Bindungen schließen, während für den Carbonyl-Komplex aufgrund von 13C-NMR-Daten eine überwiegend kovalente Ni—CH3-Bindung anzunehmen ist. Die Befunde stehen mit folgender Reihe zunehmender Akzeptorstärke im Einklang: Ni(CDT) 〈 Ni(C2H4)2 〈 Ni(CO)3.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180126
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