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  • Chemistry  (96)
  • Carbonyl complexes  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Synthesis and Structure of the First Carbyne Complex Functionalized Zwitterionic α-Carbenium Phosphinates [Tp′(CO)2M ≡ C-P(O)2-C(NR2)2] (M = Mo, W; R = Me, Et) (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 579-582 
    Details
    ISSN: 1434-1948
    Keywords: Carbyne complexes ; Molybdenum complexes ; Oxidations ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of the phosphaalkenyl-substituted carbyne complexes [Tp′(CO)2M≡C-P=C(NR2)2] (1a: M = Mo, R = Me; 1b: M = W, R = Me; 2a: M = Mo, R = Et; 2b: M = W, R = Et) with molecular dioxygen cleanly affords the orange carbyne complexes [Tp′(CO)2M≡C-P(O)2C(NR2)2] [3a: M = Mo, R = Me; 3b: M = W; R = Me; 4a: M = Mo, R = Et; 4b: M = W, R = Et; Tp′ = HB(3,5-Me2HC3N2)3], which are functionalized at the methylidyne carbon atom by an α-carbenium phosphinate moiety. The novel compounds have been characterized by IR, 1H-, 13C-, and 31P-NMR spectroscopy. In addition, the molecular structure of 4a has been determined by a single-crystal X-ray structure analysis.
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  • 2
    Electronic Resource
    Electronic Resource
    Synthesis, Structure and Reactivity of 3,4-Dihydro-2H-1,2,4,3-triazaboroles (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1193-1198 
    Details
    ISSN: 1434-1948
    Keywords: Boron ; Triazaboroles ; Heterocycles ; Halogens ; Cyanides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,4-Dihydro-2,4-diphenyl-2H-1,2,4,3-triazaboroles 3a, 3b, and 4 were synthesized by cyclocondensation of N1,N3-diphenylformamidrazone (1) with dibromophenylborane, dibromomethylborane, and boron trichloride. 3-Chloro-3,4-dihydro-2,4-diphenyl-2H-1,2,4,3-triazaborole (4) was converted into 3,4-dihydro-2,4-diphenyl-2H-1,2,4,3-triazaborole (5) by treatment with LiAlH4. The corresponding 3-cyanato and 3-cyano derivatives 6 and 7 resulted from the reaction of 4 with AgOCN and AgCN, respectively. Compound 7 was transformed into the bis(1,2,4,3-triazaborolyl)oxane 8 by silver oxide. Compounds 1-8 were characterized by elemental analyses and spectroscopic methods (1H, 11B, and 13C NMR; IR; MS). The molecular structure of 8 was established by single-crystal X-ray diffraction analysis.
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  • 3
    Electronic Resource
    Electronic Resource
    Reactivity of Carbonyl-Functionalized Phosphaalkenes RC(O)P=C(NMe2)2 (R = tBu, Ph) towards Electrophiles (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2369-2381 
    Details
    ISSN: 1434-1948
    Keywords: Alkylation ; Carbonyl complexes ; Lewis acids ; Phosphaalkenes ; Protonation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the carbonyl-functionalized phosphaalkenes RC(O)P=C(NMe2)2 [R = tBu (2a), Ph (2b)] with protic acids and alkylating reagents occurred at the two-coordinate phosphorus atom to give the phosphanyl-substituted carbocations 3a,b and 4a,b. In contrast, treatment with Me3SiOSO2CF3 resulted in attack at the oxygen atom by the silyl group, and the formation of [RC(OSiMe3)=PC(NMe2)2]SO3CF3 (5a,b). Similarly, the Lewis acids B(C6F5)3, Al(tBu)2Cl and AlMe3 were ligated to the oxygen atom of the carbonyl group. Two equivalents of GaMe3 were added to the oxygen and phosphorus atom of the phosphaalkene to yield the thermolabile complexes [RC(OGaMe3)=P(GaMe3)C(NMe2)2] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)4], [Fe2(CO)9] or [{(Z)-cyclooctene}Cr(CO)5] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)P{M(CO)n}C(NMe2)2] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical transformations reported here underline the versatile chemistry of phosphaalkenes and emphasize a relationship between carbonyl-functionalized phosphaalkenes and the well-investigated class of phosphorus ylides. X-ray structures of compounds 6b, 7b*, 10a, 11a and 12a are reported.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Metalloarsaalkene [(η5-C5Me5)(CO)2FeAs=C(NMe2)2] as a Ligand in Carbonylchromium, -iron, and -nickel Complexes (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 55-59 
    Details
    ISSN: 1434-1948
    Keywords: Arsaalkenes ; Arsenic ligands ; Carbonyl complexes ; Chromium ; Iron ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of equimolar amounts of the metalloarsaalkene [(η5-C5Me5)(CO)2FeAs=C(NMe2)2] (1) with the carbonyl complexes [Ni(CO)4], [Fe2(CO)9], and [{(Z)-cyclooctene}Cr(CO)5], respectively, affords the adducts [(η5-C5Me5)(CO)2FeAs{M(CO)n}=C(NMe2)2] with [M(CO)n] = [Ni(CO)3] (2); [Fe(CO)4] (3), and [Cr(CO)5] (4). These feature η1 coordination of the arsaalkene ligand via the arsenic atom. The molecular structures of the complexes 3 and 4 have been determined by X-ray diffraction analyses.
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  • 5
    Electronic Resource
    Electronic Resource
    Reactivity of Ferriophosphaalkene [(η5-C5Me5)(CO)2Fe-P=C(NMe2)2] and Ferrioarsaalkene [(η5-C5Me5)(CO)2Fe-As=C(NMe2)2] Towards Trimethylaluminium, -gallium and -indium (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1607-1611 
    Details
    ISSN: 1434-1948
    Keywords: Arsaalkenes ; Phosphaalkenes ; Aluminium ; Gallium ; Indium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of equimolar amounts of the ferriophosphaalkene [(η5-C5Me5)(CO)2FeP=C(NMe2)2] (1a) or the ferrioarsaalkene [(η5-C5Me5)(CO)2FeAs=C(NMe2)2] (1b) with trimethylaluminium, trimethylgallium and trimethylindium afforded the adducts [(η5-C5Me5)(CO)2FeE{MMe3}C(NMe2)2] with E = P; M = Al (2a), Ga (3a), In (4a) and E = As; M = Al (2b), Ga (3b), and In (4b). These compounds feature η1-coordination of the phosphaalkene or the arsaalkene ligand towards the Lewis acid via the pnictogen atom. The molecular structures of 2a and 3a were elucidated by X-ray diffraction analyses.
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  • 6
    Electronic Resource
    Electronic Resource
    Preparation, Structure and Reactivity of 2-Chloro-, 2-Fluoro- and 2-Iodo-2,3-dihydro-1H-1,3,2-diazaboroles (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1145-1152 
    Details
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Halogens ; Isocyanides ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of differently substituted 2-chloro-, 2-fluoro- and 2-iodo-2,3-dihydro-1H-1,3,2-diazaboroles have been prepared by various methods. 1,3-Di-tert-butyl-2-fluoro-2,3-dihydro-1H-1,3,2-diazaborole (3a), 1,3-di-tert-butyl-2-chloro-2,3-dihydro-1H-1,3,2-diazaborole (5a), 1,3-bis(2,6-dimethyl-phenyl)-2-chloro-2,3-dihydro-1H-1,3,2-diazaborole (5b), 2-chloro-4,5-dimethyl-1,3-dineopentyl-2,3-dihydro-1H-1,3,2-diazaborole (5c), and 1,3-di-tert-butyl-2-iodo-2,3-dihydro-1H-1,3,2-diazaborole (6a) were formed from the corresponding lithiated Z-1,2-diaminoethenes, by treatment with BF3·OEt2, BCl3, or BI3 in n-hexane. Compounds 3a, 5a, and 5b are also available by sodium amalgam reduction of the adduct (tBu)(BF3)N=CH-CH=N(BF3)(tBu) (2a), and the borolium salts [RNa=CH-CH=Nb(R)BCl2]X (Na-B) (4a: R = tBu, X = BCl4 and 4b: R = 2,6-Me2C6H2, X = Cl) respectively. The iodo derivative (2,6-Me2C6H2)-Na-CH=CH-Nb(2,6-Me2C6H2)BI (Na-B) (6b) was synthesized in a redox reaction between the 1,4-diazabutadiene 1b and BI3. The novel compounds were characterized by 1H-, 11B- and 13C-NMR spectroscopy, as well as by an X-ray structure analysis of 6b.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1998/98047_s.pdf or from the author.
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  • 7
    Electronic Resource
    Electronic Resource
    Synthesis and Structure of 2-Hydro-, 2-Alkyl-, 2-Alkynyl-, and 2-Stannyl-2,3-dihydro-1H-1,3,2-diazaboroles (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 491-497 
    Details
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Hydrides ; Tin ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (4a) and 1,3-bis(2,6-dimethylphenyl)-2,3-dihydro-1H-1,3,2-diazaborole (4b) were formed by the reaction of the corresponding 2-bromo or 2-iodo derivatives 1a and 2b with LiAlH4. Treatment of 1a with n-butyllithium afforded 2-n-butyl-1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (5a), whereas 1,3-di-tert-butyl-2-cyano-2,3-dihydro-1H-1,3,2-diazaborole (3a) was converted into the 2-tert-butyl derivative 6a or the 2-ethynyl-1,3,2-diazaborole 7a by means of tert-butyllithium or by the ethylenediamine adduct of lithium acetylide. Similarly, 1,3-di-tert-butyl-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8a) and 1,3-bis(2,6-dimethylphenyl)-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8b) were accessible from 1a or 2b and trimethylstannyllithium. In the complex 9a the compound 3a serves as an η1 ligand towards the [Cr(CO)5] unit via the cyano group. These novel compounds were characterized by 1H-, 11B-, 13C-, and 119Sn-NMR spectroscopy, as well as by X-ray structure analyses of 4b, 8a, and 9a.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Übergangsmetall-Schwefelylid-Komplexe, VIII. Peripheriereaktionen an der Methylgruppe in komplexiertem l-Methyl-3,5-diphenylthiabenzol-l-oxid (1979)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3828-3841 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Sulfur Ylide Complexes, VIII. Reactions at the Methyl Group in Complexed 1-Methyl-3,5-diphenylthiabenzene 1-OxideWith n-butyllithium 1-methyl-3,5-diphenylthiabenzene 1-oxide complexes 1a-c2) are metallated at the methyl group. The obtained lithiumorganics are alkylated by electrophiles like CH3I, C3H5Br, PhCH2Br, Me3SiCl, Me3GeCl, Me3SnCl, and CH3HgCl. This reaction is accompanied by dialkylation to a certain degree. In some cases alkylation of 1a-c can also be realized in the two-phase system NaOH/CH2Cl2.
    Notes: Die 1-Methyl-3,5-diphenylthiabenzol-l-oxid-Komplexe la-c2) werden durch n-Butyllithium an der Methylgruppe lithiiert. Die entstehenden Lithiumorganyle werden mit Elektrophilen wie CH3I, C3H5Br, PhCH2Br, Me3SiCl, Me3GeCl, Me3SnCl und CH3HgCl alkyliert. Hierbei wird in gewissem Umfang auch Dialkylierung beobachtet. In einigen Fällen ist die Alkylierung von la-c auch im Zweiphasensystem NaOH/CH2Cl2 durchführbar.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19791121208
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  • 9
    Electronic Resource
    Electronic Resource
    N-Boryl- und N-Silylketimine als Komplexliganden (1974)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 547-551 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N- and N-Silylketimines as Complex LigandsN(Diethylboryl)- and N-(trimethylsilyl)ketimine react with bis(benzonitrile)palladium dichloride in good yields to afford the yellow N-boryl- and N-silyketimine complexes, [(C6H5)2CNB(C2H5)2]2PdCl2 and [(C6H5)2CNSi(CH3)3] 2PdCl2, respectively. Triphenyl-phosphine substitutes the ketimines to give trans-[(C 6H5)3P]2PdCl2. As 11B n.m.r. and i. r. spectroscopic investigations show, in both complexes the ketimine molecules seem to be coordinated to the palladium by the C=N-group. A possible bond of the N-borylketimine via the BN-π-system can be excluded.
    Notes: N-(Diäthylborly)- und N (Trimethylsilyl)diphenylketimin reagieren mit Bis(benzonitril)-palladiumdichlorid in guten Ausbeuten zu den gelben N-Boryl- bzw. N-Silylketimin Komplexen [(C6H5)2CNB(C2H5)2]2PdCl2 und [(C6H 5)2CNSi(CH3)3]2PdCl2. Triphenylphosphin substituiert die Ketimine unter Bildung von trans-[(C6H5)3P]2PdCl2. Wie 11B-NMR- und IR-spektroskopische Untersuchungen zeigen, scheinen in beiden Komplexen die Ketimini-Moleküle durch die C=N-Gruppe an das Palladium koordiniert zu sein. Eine mögliche Bindung des N-Borylketimins über das BN-π-System kann ausgeschlossen werden.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19741070220
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  • 10
    Electronic Resource
    Electronic Resource
    Übergangsmetall-Schwefelylid-Komplexe, VII. η5-Thiacyclohexadienyl-1-oxid als neuartiger Ligand in komplexen Anionen (1979)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 99-106 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Sulfur Ylide Complexes, VII. η5-Thiacyclohexadienyl 1-Oxide as Novel Ligand in Complex AnionsFrom the reaction of syn-tricarbonyl(1-methyl-3,5-diphenylthiabenzene 1-oxide)chromium, molybdenum, and -tungsten (2a-c) with disodium tetracarbonylferrate or lithium diphenyl-phosphide the alkali salts of complex anions (3a-c, 5a-c) are obtained. They contain the novel ligand η5 -thiacyclohexadienyl 1-oxide. The alkali salts are converted into the tetraethylammonium salts 4a-c, which are characterized by analytical and spectroscopical data.
    Notes: Bei der Umsetzung von syn- Tricarbonyl(1-methyl-3,5-diphenylthiabenzol-1-oxid)chrom, -molybdän und-wolfram (2a-c) mit Dinatrium-tetracarbonylferrat oder Lithium-diphenylphosphid entstehen die Alkalisalze komplexer Anionen mit η5-Thiacyclohexadienyl-1-oxid als neuartigem Liganden (3a-c, 5a-c). Diese werden in die Tetraethylammoniumsalze 4a-c übergeführt und als solche auf analytischem und spektroskopischem Wege charakterisiert.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19791120110
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