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  • 1
    Electronic Resource
    Electronic Resource
    1-Sila-3-alumina-4-aluminatacyclopentan mit Al-Al-Bindung und C2Al2Si-Heterocyclus (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2637-2641 
    Details
    ISSN: 0009-2940
    Keywords: Aluminium-aluminium bond ; C2Al2Si heterocycle ; Aluminium, three- and fourfold coordinated ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Sila-3-alumina-4-aluminatacyclopentane with an Al-Al Bond and a C2Al2Si HeterocycleTetrakis[bis(trimethylsilyl)methyl]dialuminium(4) (1) with an aluminium-aluminium bond reacts in the presence of tetramethylethylenediamine (TMEDA) with the sterically highly shielded bases bis(trimethylsilyl)methyllithium or bis(dimethylphosphanyl)methyllithium to yield under deprotonation of a methyl group a carbanionic species, which is stabilized by an interaction with one of the coordinatively unsaturated Al atoms. The five-membered heterocycle 5 is formed containing two Al, one Si and two C atoms. The Al-Al bond remains uncleaved. Interestingly, 5 crystallizes in different crystals with and without crystal ether, which were both characterized by crystal-structure determinations. The Al-Al bond length in 5 [264.1(2) and 266.5(3) pm, respectively] is only slightly changed in comparison to the neutral starting compound 1 (266.0 pm). Under similar conditions the sterically less demanding ethyllithium leads to a β-elimination and addition of the thereby formed LiH to one of the two Al atoms to give the recently published hydridodialuminate(5) Li(TMEDA)2+ [R2Al-AlHR2]- (2).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931261211
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Umsetzung von Isothiocyanaten und Isonitrilen mit R2Al-AlR2 [R = CH(SiMe3)2]; ein- und zweifache Insertion von Isonitril in die Aluminium-Aluminium-Bindung (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1587-1592 
    Details
    ISSN: 0009-2940
    Keywords: Al-Al bond ; insertion of isonitriles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of Isothiocyanates and Isonitriles with R2Al-AlR2 [R = CH(SiMe3)2]; Single and Double Insertion of Isonitrile into the Al-Al BondTetrakis[bis(trimethylsilyl)methyl]dialuminium(4) 1 reacts with phenyl or tert-butyl isothiocyanate with cleavage of the C = S double bond. Two compounds are formed: R2Al-S-AlR2 [R = CH(SiMe3)2] 3 and R2Al-C(NR')-AlR2 (4 R' = C6H5; 5 R'= CMe3) with a sulfur atom or an isonitrile group inserted between the aluminium atoms. Compounds 4 and 5 were isolated in high yield by the reaction of 1 with the appropriate isonitriles. By using an excess of phenyl isonitrile a dark red compound 6 is obtained with two isonitrile units inserted into the Al-Al bond and formation of a C-C single bond. According to crystal structure determinations of 4 and 6 a three-membered heterocycle is formed by the interaction of the nitrogen lone-pair to one of the Al atoms in 4, while in 6 both Al atoms are four-coordinated by bonding to a nitrogen and a carbon atom with formation of two across the C-C bond anellated four-membered heterocycles. As shown by NMR spectroscopy the molecular structure of 4 with one stereochemically saturated and one unsaturated Al atom is unchanged in solution even upon heating to 100°C.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270906
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    Paper (German National Licenses)
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