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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LIV. Synthesis of Transition Metal Carbonyl Ylide Complexes from Transition Metal Carbonyl Carbene ComplexesSecondary und tertiary alkylphosphines PX3 [X3 = (CH3)3, (C2H5)3, (n-C4H9)3, (CH3)2H] react with (alkoxycarbene)- or (alkylthiocarbene)pentacarbonyl complexes of chromium(0) and tungsten(0),(CO)5Cr[C(OCH3)C6H5], (CO)5W[C(OCH3)CH3] and (CO)5W[C(SCH3)CH3], at low temperatures to give the corresponding ylidepentacarbonylmetal complexes (CO)5M[C(PX3)(YCH3)(Z)] (M = Cr, W; Y = O, S; Z = CH3, C6H5) under addition of the phosphines to the carbene carbon atom. The structures of the pale yellow, diamagnetic, and partially very thermolabile compounds were established by analysis, i.r., n.m.r., and mass spectra. The partial thermal conversion of (CO)5Cr[C(P(CH3)2H)(OCH3)(C6H5)] in acetone was shown to yield (CO)5Cr{P(CH3)2[CH(OCH3)(C6H5)]}.
    Notes: Durch Umsetzung sekundärer und tertiärer Alkylphosphine PX3 [X3 = (CH3)3, (C2H5)3, (n-C4H9)3, (CH3)2H] mit den (Alkoxycarben)- bzw. (Alkylthiocarben)pentacarbonyl-Komplexen von Chrom(0) und Wolfram(0), (CO)5Cr[C(OCH3)C6H5], (CO)5W[C(OCH3)CH3] und (CO)5W[C(SCH3)CH3], bei tiefen Temperaturen wurden unter Addition der Phosphine an das Carbenkohlenstoffatom entsprechende Ylid-pentacarbonylmetall-Komplexe (CO)5 M[C(PX3) (YCH3)(Z)] (M = Cr, W; Y = O, S; Z = CH3, C6H5) erhalten. Die Strukturen der schwach gelblichen, diamagnetischen, z T. sehr thermolabilen Verbindungen wurden durch Analyse, IR-, NMR- und Massenspektren gesichert. Die partielle thermische Reaktion von (CO)5Cr[C(P(CH3)2H)(OCH3)(C6H5)] in Aceton zu (CO)5Cr{P(CH3)2[CH(OCH3)(C6H5)]} wurde nachgewiesen.
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  • 2
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXIX. Isomerism of cis- and trans-(Alkoxycarbene)tetracarbonyl(phosphine)metal Complexes and Dependence of the Equilibrium ConstantsSolutions of cis- and trans-(alkoxycarbene)tetracarbonyl(phosphine)metal complexes, (CO)4M(PR3)[COR′)R″] [M=Cr, W; R3=(CH3)3, (C2H5)3, (n-C4H9)3, (n-C8H17)3, (i-C2H7)3, (C6H11)3, (C2H5)2C6H5, (C6H5)2C2H5, (C6H5)3, (p-C6H4CH3)3, (p-C6H4F)3, (m-C6H4F)3; R′=CH3, C2H5; R″=CH3, C2H5, i-C3H7, C6H7, C6H5] on heating isomerize to an equilibrium situation. The equilibrium constants are dependent upon the solvent, the central metal, the phosphine group and the carbene ligand.
    Notes: cis-u. trans-(Alkoxycarben)tetracarbonyl(phosphin)metall-Komplexe, (CO)4M(PR3)[(OR′)R′] [M=Cr, W; R3=(CH3)3, (C2H5)3, (n-C4H9)3, (n-C8H11)3, (C3H5)3, (C 6H11)3, (C2H5)2C6H5, (C2H5)2C2H5, (C6H5)3, (p-C6H4CH3)3, (p-C6H4F)3, (m-C 6H4F)3; R′=CH3, C2H5; R′=CH3, C2H5, i-C3H7, C6H5] isoerisieren beim Erwärmen in Lösung bis zu einem Gleichgewichtszustand. Die lage dieses Isomerisierungsgleichgewichts ist durch die Wahl des Lösungsmittels. des Zentralmetalls der Phosphingruppe und des Carbenliganden beeinflußbar.
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  • 3
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbyne Complexes, XVII. Ring-substituted trans-Bromotetracarbonyl(phenylcarbyne) Complexes of Chromium and TungstenThe preparation and spectroscopic properties of a series of ring-substituted trans-bromotetra-carbonyl(phenylcarbyne) complexes Br(CO)4MCR [M = Cr, W; R = C6H4N(CH3)2-(p), C6H4CH3-(p), C6H4OCH3-(p), C6H2(CH3)3-(2,4,6), C6H4CF3-(p), C6H4C6H5-(o), C6H3Cl2-(2,6), C6Cl5] are described. The influence of the substituents on the vCO absorptions and on the 13C n. m. r. signals is discussed. The X-ray structure analysis of trans-Br(CO)4CrCC6H4CF3-(p) reveals the extremely short Cr—Ccarbyne bond length of 168 ± 2 pm.
    Notes: Die Darstellung und die spektroskopischen Eigenschaften einer Reihe von ringsubstituierten trans-Bromotetracarbonyl(phenylcarbin)-Komplexen Br(CO)4MCR [M = Cr, W; R = C6H4N(CH3)2-(p), C6H4CH3-(p), C6H4OCH3-(p), C6H2(CH3)3-(2,4,6), C6H4CF3-(p), C6H4C6H5-(o), C6H3Cl2-(2,6), C6Cl5] werden beschrieben und der Einfluß der Substituenten auf die vCO-Absorptionen und die 13C-NMR-Signale diskutiert. Die Röntgenstrukturanalyse von trans-Br(CO)4CrCC6H4CF3-(p) ergibt für die Cr—CCarbin-Bindung den extrem kurzen Abstand von 168 ± 2 pm.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2459-2467 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXXIV. Reversible Addition of Tertiary Phosphines on Pentacarbonyl(methoxymethylcarbene) Metal ComplexesThe reaction of tertiary phosphines PR3 [PR3 = P(C4H9)3, P(C2H5)2C6H5, P(i-C3H7)3] with pentacarbonyl(methoxymethylcarbene)metal complexes of chromium(O) and tungsten(O), (CO)5Cr[C(OCH3)] and (CO)5W[C(OCH3)], at low temperatures results in a reversible addition of the phosphine to the carbene ligand. The addition-dissociation-equilibrium constants depend on the temperature, the solvent, the phosphine, and the central metal.
    Notes: Bei der Umsetzung von tertiären phosphinen PR3 [PR3 = P(C4H9)3. P(C2H5)2 C6H5. P(i-C3H7)3] mit Pentacarbonyl(methoxymethylcarben)chrom(O) bzw. -wolfram(O). (CO)5Cr[C(OCH3)CH3] bzw. (CO)5W[C(OCH3)CH3], bei tiefen Temperaturen erfolgt eine Gleichgewichtskonstanten hängen von der Temperatur, dem Lösungsmittel, der Art des Phosphins und des Zentralmetalls ab.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2080-2093 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallaheterocumulenes, IV. 2-Azaallylidene Complexes  -  Novel Compounds with a Bent CNCR2 Fragment as Complex Ligand(2-Azoniaallenylidene)pentacarbonyltungsten tetrabromoaluminate complexes [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e)) Which are synthesized by the reaction of (CO)5W[C(OEt)N=CR2] (1) with AlBr3, react with freshly distilled tetrahydrofuran to give neural trans-bromo(2-azaallylidene) complexes trans-Br(CO)4W(CNCR2) (3) and small amounts of (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). The compounds 4 correspond to the product of a reductive dimerization of two cations 2. If 1b (or the corresponding methoxy compound 5) reacts with BBr3 instead of AlBr3/THF 4b is the main product. The spectroscopic data of 3 and the results of an X-ray analysis of 3b show that the replacement of a CO ligand in the cations 2 by Br- with formation of 3 results in a drastic change of the bonding situation within the CNCR2 ligand. 3a-e are the first compounds in which a strongly bent CNCR2 fragment functions as a complex ligand. The aminocarbyne complex trans-Br(CO)4W≡CNPh2 (7) was synthesized by BBr3-induced fragmentation of (CO)5W[C(NPh2)N=C(Ph)OMe] (6).
    Notes: (2-Azoniaallenyliden)pentacarbonylwolfram-tetrabromoaluminat-Komplexe [(CO)5W(CNCR2)]+AlBr4- (2-AlBr4) (CR2=C(C6H4Br-4)2 (a), CPh2 (b), C(C6H4OMe-4)2 (c), C(C6H4)2O (d), C(2,4,6-C6H2Me3)2 (e))  -  darstellbar durch Umsetzung von (CO)5W[C(OEt)N=CR2] (1) mit Albr3  -  reagieren mit frisch destillierten Tetrahydrofuran zu neutralen trans-Bromo(2-azaallyliden)-Komplexen trans-Br(CO)4W(CNCR2) (3) und wenig (CO)5W—C≡N—[CR2]2—N≡C—W(CO)5 (4). Die Verbindungen 4. entsprechen dem Produkt einer reduktiven Dimerisierung zweier Kationen 2. 4b wird zum Hauptprodukt der Umsetzung, wenn 1b (oder der entsprechende Methoxy-Komplex 5) mit BBr3 anstatt AlBr3/THF umgesetzt wird. Wie die spektroskopischen Daten von 3 sowie die Ergebnisse der an 3b durchgeführten Röntgenstrukturanalyse zeigen, führt der Austausch eines CO-Liganden in den Kationen 2 gegen Br- unter Bildung von 3 zu einer drastischen Veränderung der Bindungsverhältnisse im CNCR2-Liganden. 3a-e sind die ersten Verbindungen, in denen ein stark gewinkeltes CNCR2-Fragment als Komplexligand fungiert. Durch BBr3-induzierte Fragmentierung von (CO)5W[C(NPh2)N=C(Ph)OMe] (6) wurde der Aminocarbin-Komplex trans-Br(CO)4W≡CNPh2 (7) dargestellt.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 811-814 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The cationic [3,3-bis(tert-butyl)-2-azoniaallenylidene]pentacarbonyl complexes [(CO)5M(CNC(tBu)2)]⊖ AlBr4⊕ (2) [M=Cr (a), W (b)] which are synthesized by the reaction of (CO)5M-[C(OEt)N=C(tBu)2] (1) with AlBr3, react with tetrahydrofuran via addition of Br⊖ to give the isocyanide complexes (CO)5M-C≡N-C(tBu)2Br (3). Under nitrogen at room temperature, 3b decomposes in solution within ca. two hours to give the binuclear diisocyanide complex [(CO)5W-C≡N]2C(tBu)2 (4b). When the same conditions are applied to solutions of 3b in the presence of oxygen or of galvinoxyl 3b is stable. The structure of 4b was confirmed by an X-ray analysis.
    Notes: Die kationischen [3,3-Bis(tert-butyl)-2-azoniaallenyliden]pentacarbonyl-Komplexe [(CO)5M(CNC(tBu)2)⊖ (2) [M=Cr (a), W (b)] - darstellbar durch Umsetzung von (CO)5M[C(OEt)- N=C(tBu)2] (1) mit AlBr3 - reagieren mit Tetrahydrofuran unter Addition von Br⊕ zu den Isocyanid-Komplexen (CO)5M - C≡N-C(tBu)2Br (3). Bei Raumtemperatur zersetzt sich 3b unter Stickstoff in Lösung innerhalb von ca. zwei Stunden zu dem zweikernigen Diisocyanid-Komplex [(CO)5W-C≡N]2C(tBu)2 (4b), in Gegenwart von Sauerstoff oder von Galvinoxyl ist 3b unter ansonsten gleichen Bedingungen stabil. Die Struktur von 4b wurde durch eine Röntgenstrukturanalyse gesichert.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2519-2524 
    ISSN: 0009-2940
    Keywords: 1-Aza-2-azoniaallene cations ; Carbodiimides ; 1H-1,2,4-Triazolium salts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Aza-2-azoniaallene cations 3, prepared in situ from geminal (chloroalkyl)azo compounds 2, react with carbodiimides 4 to give 4,5-dihydro-5-imino-1H-1,2,4-triazolium salts 7. An X-ray structural analysis was carried out for 71. According to AM1 calculations the cycloaddition of carbodiimides to 1-aza-2-azoniaallene cations occurs in a nonconcerted manner via cyanamidium cations 5 as intermediates. Hetero-Wagner-Meerwein rearrangements of the primary cycloadducts 6 provide the final products 7.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1149-1156 
    ISSN: 0009-2940
    Keywords: Selenoaldehyde complex ; Thioselonocarboxylic ester complexes ; Selenetane complex ; Dihydrodiselenine complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyltungsten-coordinated selenobenzaldehyde, [(CO)5W{Se=C(Ph)H}] (1), reacts with tBu-C≡C-SMe (2) by insertion of the C≡C into the Se=C bond to form in a highly regio- and stereoselective manner the α,β-unsaturated thioselonocarboxylic ester complex (Z)(C=C)-[(CO)5W{≡1-Se=C(SMe)C(tBu)=C(Ph)H}] (3). The thioselonocarboxylic ester ligand is cleaved intact from the metal by treatment of 3 with [NEt4]Br. Three complexes are formed in the reaction of 1 with Me-C≡C-SMe (5): the thioselonocarboxylic ester complex [(CO)5W{≡1-Se=C(SMe)C(Me)=C(Ph)H}] (6) as a mixture of the (E) and (Z)(C=C) isomers, a selenetane complex (7) and a dihydrodiselenine complex (8). The product distribution depends on the ratio 1:5 and on the solvent. The reaction of 1 with the bis(organylthio)alkynes RS-C≡C-SR (9) [R = Me (a), iPr (b), 2,6-C6H3Me2 (c)] yields mixtures of the (E) and (Z)(C=C) isomers of the α,β-unsaturated α-organylthio thioselonocarboxylic ester complexes [(CO)5W{≡1-Se=C(SR)C(SR)=C(Ph)H)] (10a-c). In contrast, the reaction of 1 with tert-butoxyethyne, H-C≡C-OtBu (11), affords a bis(pentacarbonyltungsten) 5,6-dihydro-1,2-diselenine complex (12). Compound 12 is probably formed by consecutive reaction of 1 with 11 to give the selonocarboxylic ester complex [(CO)5W{≡1-Se=C(OtBu)C(H)=C(Ph)H}] which then further reacts as a heterodiene by highly regioselective [4 + 2] cycloaddition with the Se=C bond of a second molecule of 1 to give 12. In the reaction of 1 with 5 and 9a the isomer with a trans arrangement of C(=Se)SMe and Ph is the kinetically controlled reaction product [(E)-6 and (Z)-10a, respectively]. The formation of (E)-6 and (Z)-10a is followed by isomerization until an (E)/(Z) equilibrium is reached. Complexes 3 and 7 were characterized by X-ray structural analyses.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1475-1482 
    ISSN: 0009-2940
    Keywords: Allenylidene complexes ; Alkynyl complexes ; Cyclobutenylidene complexes ; Cycloadditions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyl(allenylidene)chromium and -tungsten, [(CO)5—M=C=C=CR2] (M=Cr, R=C6H4CH3-p(1a), C6H4OCH3 (1b); M=W, R=C6H4CH3-p (1c), react with the alkynyl complexes [Cp(CO)2Fe—C≡CR′] (R′ = nBu (2), Ph (4)), [Cp*(CO)2Fe—C≡CnBu] (6), [Cp(CO){P(OMe)3}-Fe—C≡CnBu] (8) and [Cp(PPh3)Ni—C≡CnBu] (10) by cycloaddition of the C≡C bond of the alkynyl complexes to the Cα=Cβ bond of the allenylidene ligand to give 3a-c), (5), (7), and respectively. The cycloaddition is highly selective. The spectroscopic data of these 1,3-heterobinuclear complexes indicate a delocalized π-system (M=Cr, W; Y=[Fe(CO)2Cp], [Fe(CO)(P{OMe}3)Cp], [Fe(CO)2Cp*], [Ni(PPh3)-Cp]). X-ray structural analyses of the compounds 3a, 9a, and 11c reveal a “butterfly” conformation of the four-membered ring. Its puckering angle is 142° (3a), 152° (9a), and 151° (11c). All Complexes exhibit a moderate to strong negative solvatochromic behavior. The extent of the solvatochromic effect depends on [(CO)5M] and Y and considerably decreases when C=CR2 is replaced by e.g. CMe2.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 479-488 
    ISSN: 0009-2940
    Keywords: Heterobimetallic complexes ; Carbene complexes ; Alkynes ; Coupling reaction ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequential reaction of the dimethylamino(trimethylsilylethylnyl)carbene complexes [(CO)5M'=C(NMe2)C≡CSiMe3] [M' = W (1a)] with KF/THFMeOH, nBuLi and transition metal halides, [XMLn], affords heterobimetallic propynyliden complexes of the type [(CO)5M'=C(N-Me2)C≡CMLn] [MLn = Ni(PPh3) Cp (4a, b). Ni(PMe2Ph)2- {Mes) (Mes=2,4,6-C6H2Me3) (5a), Rh(CO)(PPh3)2 (6a), Fe(CO)2Cp (7a,b)]. In contrast, reaction of 1a with MeLi · LiBr and [IFe(CO)2Cp] yields the novel N-metallated complex [(CO)5W=C{N(ME)Fe(CO)2Cp}C≡CSiMe3] (8a). The complexes [(CO)5M'=C(NMe2)C≡CMLn=Fe(CO)2Cp (7a, b), Ru(CO)2Cp (10a,b), Ru(CO)(PPh3)Cp (11a), Mn(CO)5 (12a), Re(CO)5 (13a)] are accessible by Pd-catalyzed coupling of the C-stannylated carbene complexes [(CO)5M'=C-(NMe2)C≡CSnBu3] (9a, b) with [XMLn]. The related monomethylaminocarbene complexes [(CO)5M'=C(NHMe)C≡ CSnBu3] (16a, b), obtained by stannylation of [(C))5M'=C(NHMe)C=CH] (15a, B) with Bu3SnNEt2, react with [IFe(CO)2Cp] to give the bimetallic complexes [(CO)5M'=C(NHMe)C≡CFe(CO)2Cp] (17a, b). The complexes 4a, 5a, 7a and 10a were characterized by X-ray structural analysis. The spectroscopic and structural data suggest that the two metal centers in 4-7, 10-13, and 17 interact only weakly.
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