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  • 1990-1994  (2)
  • 1
    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
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  • 2
    ISSN: 0044-2313
    Keywords: Methylene bridged dialuminium compounds ; reaction with LiCH(PMe2)2 ; Al2C2P heterocycle ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reaction of [(Me3Si)2CH]2Al—CH2—Al [CH(SiMe3)2]2 with LiCH(PMe2)2; Formation of a Five-membered Al2C2P HeterocycleThe recently synthesized methylene bridged dialuminium compound [(Me3Si)2CH]2Al—CH2—Al [CH(SiMe3)2]2 3 reacts with one equivalent of LiCH(PMe2)2 in the presence of TMEDA to give an adduct with one aluminium atom coordinated by the carbanionic carbon atom and the second one coordinated by one phosphorus atom. A five-membered heterocycle 5 is formed, which was characterized by a crystal structure determination showing a strongly bent ring with the phosphorus atom located above the plane of the four remaining atoms (Al2C2). 5 is unstable in ethereal solution decomposing under ether cleavage to the educt 3 and the diphosphinomethane derivative CH2(PMe2)2.
    Notes: Die methylenverbrückte Dialuminiumverbindung [(Me3Si)2CH]2Al—CH2—Al [CH(SiMe3)2]2 3 reagiert mit einem Äquivalent LiCH(PMe2)2 in Gegenwart von TMEDA unter Anlagerung des carbanionischen Kohlenstoffatoms und eines der beiden Phosphoratome an seine beiden ungesättigten Metallatome. Dadurch entsteht ein fünfgliedriger Al2C2P-Heterozyklus 5, der im Festkörper eine sehr starke Winkelung aufweist. 5 ist in etherischer Lösung nicht beständig und ergibt unter Etherspaltung neben dem Edukt 3 das Diphosphanomethan CH2(PMe2)2.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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