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  • Arsaalkenes  (3)
  • Carbonyl complexes  (2)
  • 6,7,13,14-Tetrasiladispiro[4.2.4.2]tetradeca-1,3,9,11-tetraene derivatives  (1)
  • 1
    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.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 2
    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.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 3
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 4
    Electronic Resource
    Electronic Resource
    Transition Metal-Substituted Arsaalkenes, II. Synthesis, Structure and Reactivity of the Arsaalkenes RAs=C(NMe2)2 [R = Me3Si, (η5-C5Me5)(CO)2Fe] and the 1,2-Dihydroarsete (η5-C5Me5)(CO)2-Fe (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 223-226 
    Details
    ISSN: 0009-2940
    Keywords: Arsaalkenes ; Carbonyliron complexes ; Arsete, 1,2-dihydro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of equimolar amounts of thiuronium salt [(Me2N)2C-SMe]I (1, with LiAs(SiMe3)2 · 2 THF (2) afforded arsaalkene Me3SiAs=C(NMe2)2 (3). Combination of 3 with (η5-C5Me5)(CO)2 FeBr led to the formation of (η5-C5Me5)(CO)2-FeAs=C(NMe2)2 (4). Reaction of the latter with dimethyl fumarate gave the 1,2-dihydroarsete (η5-C5Me5)(CO)2-Fe (6). Compounds 3, 4, and 6 were characterized by means of spectroscopy (IR, 1H, 13C{1H}, 29Si{1H} NMR and mass spectrometry). The molecular structures of 4 and 6 were determined by X-ray diffraction analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290217
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  • 5
    Electronic Resource
    Electronic Resource
    Synthese von 6,6,7,7,13,13,14,14-Octamethyl-6,7,13,14-tetrasiladispiro[4.2.4.2]- tetradeca-1,3,9,11-tetraen und sein Einsatz in der π-Komplexchemie von p- und d-Block-Elementen (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2391-2399 
    Details
    ISSN: 0009-2940
    Keywords: 6,7,13,14-Tetrasiladispiro[4.2.4.2]tetradeca-1,3,9,11-tetraene derivatives ; Metallocenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of 6,6,7,7,13,13,14,14-Octamethyl-6,7,13,14-tetrasiladispiro[4.2.4.2] tetradeca-1,3,9,11-tetraene and Its Application in the Chemistry of π Complexes of p- and d-Block ElementsThe title compound 2 can be synthesized either by reaction of ([C5H5SiMe2SiMe2C5H5]2- 2 Li+) with XSiMe2SiMe2X or by an intermolecular nucleophilic substitution reaction between two molecules of ([XSiMe2SiMe2C5H5]- Li+). Isomers of 2 with allylic hydrogen atoms arise from silatropic rearrangements and therefore show “cyclopentadiene reactivity”. Reaction of the monoanion of 2 with FeCl2 yields the ferrocene 4. From the reaction of the dianion of 2 with Me5C5RuCl, the binuclear ruthenium complex 7 with Si - Si bridges in 1,2-position can be isolated; reactions with FeCl2 or Me5C5Fe(acac), with Me5C5GeCl, with SnCl2, and with PbCl2, lead to the metallocenes 6, 7, 8, and 9; in all these complexes the disilane bridges are in 1,2-position. The binuclear cobalt complex 10, in which the cyclopentadienyl rings are connected with each other by disilane bridges in 1,3-position, can be synthesized by the reaction of 2 with CO2(CO)8. The results of single-crystal X-ray structure analyses of 6 and 10 are presented. The possible conformations of the dianion of 2 are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911241103
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