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  • 1
    Electronic Resource
    Electronic Resource
    Regiospecific Hydroxylation of Metallodisilanes of the Iron Group - An Impressive Example of the Transition Metal Effect (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1585-1587 
    Details
    ISSN: 1434-1948
    Keywords: Metallodisilanes ; Oxofunctionalization ; Metallodisilandiols ; Silanetriols ; Metallosiloxanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the ferriodisilanes C5R5(OC)2Fe-Si2H5 [R = H (1a), Me (1b)] with dimethyldioxirane leads to selective insertion of oxygen into the α-Si-H bonds to yield the ferriodihydroxydisilanes C5R5(OC)2Fe-Si(OH)2-SiH3[R = H (2a), Me (2b)]. Another access to yield 2a is opened by hydrolysis of the dichloro(ferrio)disilane Cp(OC)2Fe-SiCl2-SiH3 (3a). Treatment of the pentachloro(metallo)disilanes C5H5(OC)2Fe-Si2Cl5 (4a) and C5Me5(OC)2Ru-Si2Cl5 (4b) with water results in regiospecific hydroxylation of the β-silicon atom to generate metallodisilanetriols C5R5(OC)2M-SiCl2-Si(OH)3 [M = Fe, R = H (5a); M = Ru, R = Me (5b)]. Controlled condensation of 5b with Me2Si(H)Cl leads to the novel rutheniosiloxane C5Me5(OC)2Ru-SiCl2-Si(OSiMe2H)3 (6).
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Iron and Ruthenium Fragment Substituted Disilanes C5R5(OC)2M-Si2X5 (R = H, Me; M = Fe, Ru; × = Cl, H): Synthesis, Structural and Raman Spectroscopic Characterisation, DFT Calculation (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1597-1605 
    Details
    ISSN: 1434-1948
    Keywords: Metallo-disilanes ; Ligand exchange at silicon ; Transition metal effect ; Raman spectroscopy ; Density functional theory ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the sodium metalates Na[M(CO)2C5R5] [M = Fe, R = H (1a), Me (1b); M = Ru, R = H (1c), Me (1d)] with an equimolar amount of hexachlorodisilane yields the metallo-pentachlorodisilanes C5R5(OC)2M-SiCl2-SiCl3 (2a-d), which can be converted into the pentahydrido analogues C5R5(OC)2M-SiH2-SiH3 (3a-c) via Cl/H exchange with LiAlH4. Due to the activating effect of the transition metal fragment chlorination of 3a-c with CCl4 or HCCl3 occurs at the α-silicon to give C5R5(OC)2M-SiCl2-SiH3 (4a-c). The metallo-disilanes were characterised by 1H-, 13C-, 29Si-NMR, IR and especially Raman spectroscopy. The structures of C5H5(OC)2Fe-Si2Cl5 (2a) andC5Me5(OC)2Fe-Si2H5 (3b) have been determined by X-ray analysis; 2a,b, 3a,b were theoretically described by DFT calculations.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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