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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1153-1160 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Way to Pentafluorocyclopentadienyl Anion: 1,2,3,4,5-Pentafluorocyclopentadiene1,2,3,4,5-Pentafluorocyclopentadiene (8) was obtained in three steps from hexachlorocyclopentadiene (2). It is a typical cyclopentadiene. Thus, it dimerizes reversibly already at - 78°C.
    Notes: 1,2,3,4,5-Pentafluorcyclopentadien (8) wurde in drei Stufen aus Hexachlorcyclopentadien (2) hergestellt. Es ist ein typisches Cyclopentadien. So dimerisiert es - reversibel - bereits bei - 78°C.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 1413-1416 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: coupling of a Fluoromethylidyne Ligand with Alkynes and Formation of a CF—CR—CR Ligand. Synthesis of Fe3(CO)8(μ3-CF)(μ3-CF—CR—CR)Nonacarbonyl-bis(μ3-fluoromethylidyne)triiron (4) reacts with alkynes R—C≡C—R (2a-e) and carbon-carbon bond formation to diferra-allyl clusters Fe3(CO)8(μ3-CF)(μ3-CF—CR—CR) (5a-e). The spectroscopic data of the compounds proof the existence of a μ3-fluoromethylidyne and a CF—CR—CR ligand in the molecules. The structure of Fe3(CO)8(μ3-CF)(μ3-CF—CH—CH) 5a is established by an X-ray crystal structure determination.
    Notes: Nonacarbonyl-bis(μ3-fluormethylidin)trieisen (4) reagiert mit Alkinen R—C≡C—R (2a-e), unter C—C-Bindungsknüpfung zu Diferra-Allyl-Clustern Fe3(CO)8(μ3-CF)(μ3-CF)(μ3-CF—CR—CR) (5a bis e). Die spektroskopischen Daten der Verbindungen belegen die Anwesenheit eines μ3-Fluormethylidin- und eines μ3-CF—CR—CR-Liganden. Die Struktur von Fe3(CO)8(μ3-CF)(μ3-CF—CH—CH) 5a wird durch eine Kristallstrukturuntersuchung gesichert.
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  • 3
    ISSN: 0009-2940
    Keywords: Isocyanide-bridged metal complexes ; Metal complexes as ligands ; N-Protonation (alkylation, metalation) ; Heteropentanuclear metal complexes ; Diisocyanide bridges ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coordination Chemistry with the Complex Chelating Ligands [{Fe2Cp2(CO)3)2{CN[CH2]n NC}] (n = 2, 3). Heteropentanuclear “Supercomplexes” with μ5-Diisocyanide BridgesHerrn Professor Dr. O. J. Scherer zum 60. Geburtstag gewidmet.The tetranuclear complexes [(Fe2Cp2(CO)2(μ-CO)}2(μ4-CN[CH2]nNC}] [n = 2 (2), 3 (3)] act as bidentate chelating ligands towards the Lewis-acidic metal halides MnCl2, MnBr2, FeCl2, CoCl2, NiCl2, NiBr2, CuCl2, CuBr2, ZnCl2, ZnI2, CdCl2, CdI2, HgCl2, the chloro complexes [MCl2-(NCPh)2] (M = Pd, Pt), Zn(OAc)2 · H2O, and [Mo(CO)4(η-NBD)] (NBD = 2,5-norbornadiene) to give a total of 22 pentanuclear “supercomplexes” ,6-21, which have been characterized by elemental analyses and IR and NMR (1H, 13C) spectra. Reaction of 2 with [Ni(COD)2] in CH2Cl2 gave only rise to the dichloronickel(II) species 9a. Very remarkably, the pentairon complex [(Fe2Cp2(CO)2(μ-CO)2(μ5-CN(CH2)2-NC)}]FeCl2 (7) also formed spontaneously (!) when 2 was refluxed in chloroform for several hours. The X-ray structure analysis of [{Fe2Cp2(CO)2(μ-CO))2{μ5-CN(CH2)2NC}]CdI2 (14b) confirms the twofold μ3-(C,C,N) bridging mode of a diisocyanide ligand in a cis/cis-anti-configurated [Fe2]2Cd pentanuclear system of crystallographic C2 symmetry.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 560-563 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tetrakis(trifluoromethyl isocyanide)nickel, Ni(CNCF3)4, and Bis[μ-(trifluoromethyl isocyanide)-(η-cyclopentadienyl)nickel], [Ni(μ-CNCF3)(η-C5H5)]2Tetrakis(trifluoromethyl isocyanide)nickel (3) is formed in the reaction of tetracarbonylnickel (1) and trifluoromethyl isocyanide (2). 3 is the first homoleptic trifluoromethyl isocyanide complex. The dinuclear complex [Ni(μ-CNCF3)(η-C5H5)]2 (5) is isolated in high yield from the reaction of 3 with bis(η-cyclopentadienyl)nickel (4). Its spectroscopic data proof the existence of the isocyanide bridged isomer.
    Notes: Tetrakis(trifluormethylisocyanid)nickel (3) bildet sich in guten Ausbeuten bei der Reaktion von Tetracarbonylnickel (1) mit Trifluormethylisocyanid (2). 3 ist der erste homoleptische Trifluormethylisocyanidkomplex. Der zweikernige Komplex [Ni(μ-CNCF3)(η-C5H5)]2 (5) entsteht aus 3 und Bis(η-cyclopentadienyl)nickel (4). Seine spektroskopischen Daten beweisen das alleinige Vorliegen des Trifluormethylisocyanid-überbrückten Isomeren.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 303-305 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dicarbonyl(π-pentamethylcyclopentadienyl)(trifluoromethyl isocyanide)manganese (4) has been synthesized by reaction of Cp*Mn(CO)2(η2-C8H14) (Cp*=(CH3)5C5) (3) with trifluoromethyl isocyanide (1). Cp*Mn(CO)2(CNCH3) (7) has been obtained from Cp*Mn-(CO)2(THF) (5) and CH3NC (6). Cp*Mn(CO)2(CS) (9) is formed in the reaction of 3 with CS2 (8) in the presence of triphenylphosphane. Photolysis of Cp*Mn(CO)3 (2) in the presence of excess 1 yields Cp*Mn(CNCF3)3 (10) as the final product. All these (pentamethylcyclopentadienyl)(trifluoromethyl isocyanide)manganese complexes exhibit infrared absorption bands at low wave-numbers for the NC vibrations and at high wave-numbers for the CO vibrations. The force constant of the CO vibration indicates that the trifluoromethyl isocyanide ligand is an extremely strong π-accepting ligand which exceeds even the thiocarbonyl ligand in its π-accepting ability.
    Notes: Die Synthese von Dicarbonyl(π-pentamethylcyclopentadienyl)-(trifluormethylisocyanid)mangan (4) gelingt durch Umsetzung von Cp*Mn(CO)2(η2-C8H14) (Cp*=(CH3)5C5) (3) mit Trifluormethylisocyanid (1). Cp*Mn(CO)2(CNCH3) (7) wird aus Cp*Mn-(CO)2(THF) (5) und CH3NC (6) erhalten. Cp*Mn(CO)2(CS) (9) Bildet sich aus 3 und CS2 (8) in Gegenwart von Triphenylphosphan. Cp*Mn(CNCF3)3 (10) entsteht bei der Photolyse von Cp*Mn(CO)3 (2) mit überschüssigem 1. Alle (Pentamethylcyclopentadienyl)(trifluormethylisocyanid)mangan-Komplexe zeigen niedrigliegende NC-Valenzschwingungen und hochliegende CO-Valenzschwingungen. Aus den Kraftkonstanten der CO-Valenzschwingung läßt sich die relative π-Akzeptorstärke des Trifluormethylisocyanid-Liganden abschätzen, die sogar die des Thiocarbonylliganden übertrifft.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 257-260 
    ISSN: 0009-2940
    Keywords: Chromium isocyanide complexes / Isocyanide ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cr(CO)4(CNCF3)(CNCH3) and Cr(CO)4(CNCF3) (CNC6H5), Isocyanide Complexes with +I- and - I-substituted IsocyanidesPentacarbonyl(trifluoromethyl isocyanide)chromium (1) undergoes photolytic substitution of exclusively one carbonyl ligand by THF. According to the IR spectrum, (CO)4Cr(CNCF3) (THF) (2) consists of a mixture of the trans and cis isomer. 2 reacts with methyl isocyanide (3) and phenyl isocyanide (4) forming 9CO)4Cr(CNCF3) (CNCH3) (5) and (CO)4Cr(CNCF3) (CNC6H5) (7), respectively. 5 is obtained as a mixture of the trans and cis isomer (10:1), which can be separated by chromatography. In addition, a small amount of the disubstituted compound (CO)3Cr(CNCF3) (CNCH3)2 (6) is obtained, which according to its spectroscopic data contains the CNCF3 ligand and one CNCH3 ligand in trans position. In the case of 7, the trans isomer is the only product observed. The structure of trans-5 has been established by X-ray crystal structure determination.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 773-775 
    ISSN: 0009-2940
    Keywords: Alkyne complexes ; Clusters ; Iron complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of undecacarbonyl(acetonitrile)triiron (1) with 1,4-dimethoxy-2-butyne (2) yields the alkyne complexes decacarbonyl(μ3;-η2-Verbar-1,4-dimethoxy-2-butyne)triiron (3) and nonacarbonyl(μ3;-η2;-⊥-1,4-dimethoxy-3-butyne)triiron (4). The crystal structure determination of 2 shows that the alkyne ligand is coordinated strictly parallel to one iron-iron edge.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1093-1100 
    ISSN: 0009-2940
    Keywords: Isocyanide dichlorides, functional ; (Lewis)Basic metals ; (Three component)Oxidative additions ; Iron complexes, di- and trinuclear ; Isocyanide bridges, functional ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isocyanide- and Heteroallene-Bridged Metal Complexes, IX[1,2]. - Di- and Triiron Complexes with Functional Bridging IsocyanidesThe reactions of ten mainly functional isocyanide dichlorides RN = CCl2 with Na[FeCp(CO)2] in tetrahydrofuran give mono-isocyanide derivatives [Fe2(Cp)2(CO)3CNR] (1 a-g) of [Fe-Cp(CO)2]2 in which the isocyanide occupies a bridging position. In three cases also minor amounts of diisocyanide complexes [FeCp(μ-CNR)CO]2 (2c, 2e, 8) have been isolated. The chlorocarbonyl-substituted aryl isocyanide dichlorides and pentafluorophenyl isocyanide dichloride in addition suffer (CO)Cl/ and F/ metal exchange, respectively, with formation of μ3-isocyanide-bridged triiron complexes (4 a-c, 7) via the intermediates 5 and 6, 7 has been studied by X-ray analysis.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 1445-1447 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Pentafluorophenyl Isocyanide and Its Stabilization as a Ligand in Cp*mn(CO)2(CN-C6F5)Pentafluorophenyl isocyanide, C6F5—NC, has been obtained for the first time in analytical pure from by dehalogenation of dibromo-N-(pentafluorophenyl)methanimine, C6F5—N=CBr2, with magnesium in THF. At -30°C, C6F5—NC is a crystalline, colourless solid, which readily decomposes on heating to its melting point of 13°C. On reaction with Cp*Mn(CO)2(THF),C6F5—NC can be stabilized by complexation to form Cp*Mn(CO)2(CN—C6F5), the structure of which is elucidated by a crystal structure analysis.
    Notes: Pentafluorphenylisocyanid, C6F5—NC, läßt sich durch Dehalogenierung von Dibrom-N-(pentafluorphenyl)methanimin, C6F5—N=CBr2, mit Magnesium in THF erstmalig in reiner Form darstellen. C6F5—NC ist bei -30°C ein farbloser kristalliner Feststoff, der sich oberhalb seines Schmelzpunkts von 13°C rasch zersetzt. Durch Umsetzung von C6F5—NC mit Cp*Mn(CO)2(THF) kann C6F5—NC am Komplex unter Bildung von Cp*-Mn(CO)2(CN—C6F5) stabilisiert werden, dessen Struktur durch eine Kristallstrukturanalyse aufgeklärt wird.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1223-1225 
    ISSN: 0009-2940
    Keywords: Half-sandwich complexes ; Manganese ; Trifluoromethyl isocyanide ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Half-Sandwich Complexes of Manganese with the Trifluoromethyl Isocyanide Ligand: Cp*Mn(CO)(CNCF3)(L)Photolysis of Cp*Mn(CO)2(CNCF3) (1) [Cp* = (CH3)5C5] in the presence of cis-cyclooctene (2) and THF (4) yield Cp*Mn(CO)(CNCF3)(η2-C8H14) (3) and Cp*Mn(CO)(CNCF3)(THF) (5), respectively. Reaction of 3 with CS2 in the presence of P(C6H5)3 yields Cp*Mn(CO)(CNCF3)(CS) (8). Substitution of the labile THF ligand of 5 or cis-cyclooctene ligand of (3 allows the synthesis of the complexes Cp*Mn(CO)(CNCF3)(L) (7a-f) [L = P(C6H5)3 (a), P(C2H5)3 (b), PF3 (c), CNCH3 (d), CNC6H5 (e), CNCF3 (f)].
    Notes: Bestrahlung von Cp*Mn(CO)2(CNCF3) (1) [Cp* = (CH3)5C5] mit cis-Cycloocten (2) bzw. in THF (4) liefert die Verbindungen Cp*Mn(CO)(CNCF3)(η2-C8H14) (3) bzw. Cp*Mn(CO)(CNCF3)(THF) (5). Umsetzung von 3 mit CS2 in Gegenwart von Triphenylphosphan ergibt den Thiocarbonyl-Komplex Cp*Mn(CO)(CNCF3)(CS) (8). Die Substitution des labilen THF-Liganden in 5 bzw. cis-Cycloocten-Liganden in 3 ermöglicht die Synthese weiterer gemischtsubstituierter Komplexe Cp*Mn(CO)(CNCF3)(L) (7a-f) [L = P(C6H5)3 (a), P(C2H5)3 (b), PF3 (c), CNCH3 (d), CNC6H5 (e), CNCF3 (f)].
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