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Hydroalumination of Nitriles and Isonitriles

Hydroalumination of Nitriles and Isonitriles AbstractHydroalumination of H5C6-C≡N with di(tert-butyl)aluminum hydride 1or the corresponding diethyl compound 2yielded the products tBu2Al-N=C(C6H5)H 3and Et2Al-N=C(C6H5)H 4, respectively, both of which form dimers possessing Al2N2 heterocycles with two exocyclic C=N double bonds. NMR spectroscopic data indicate the occurrence of cis/trans isomers in solutions of compound 4. The dimerization of the imide via Al-N interactions was prevented by employing the hydride [(Me3Si)2HC]2AlH 6bearing the bulky bis(trimethylsilyl)methyl substituents. Its reaction with benzonitrile yielded the compound R2Al-N=C(C6H5)H(N≡C-C6H5) 7[R = CH(SiMe3)2], in which the coordinative saturation of the aluminum atoms was achieved by adduct formation with one molecule of the starting nitrile. In these cases the C≡N triple bond inserted completely into the Al-H bond of the hydride. In contrast, the reaction of tert-butyl isonitrile afforded the product tBu2Al-C(H)=NC6H58by the insertion of its terminal carbon atom into the Al-H bond. Hence, it has a geminal arrangement of the aluminum and hydrogen atoms. Dimerization of 8yielded a six-membered heterocycle. Hydroalumination does not occur upon treatment of the hydride 1with trimethylsilylnitrile. Instead, the Si-CN bond was cleaved, and the aluminum cyanide (tBu2Al-C≡N)49was isolated in a high yield. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Zeitschrift für Naturforschung B de Gruyter

Hydroalumination of Nitriles and Isonitriles

Zeitschrift für Naturforschung B , Volume 59 (11-12): 9 – Dec 1, 2004

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References (9)

Publisher
de Gruyter
Copyright
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
ISSN
0932-0776
eISSN
1865-7117
DOI
10.1515/znb-2004-11-1239
Publisher site
See Article on Publisher Site

Abstract

AbstractHydroalumination of H5C6-C≡N with di(tert-butyl)aluminum hydride 1or the corresponding diethyl compound 2yielded the products tBu2Al-N=C(C6H5)H 3and Et2Al-N=C(C6H5)H 4, respectively, both of which form dimers possessing Al2N2 heterocycles with two exocyclic C=N double bonds. NMR spectroscopic data indicate the occurrence of cis/trans isomers in solutions of compound 4. The dimerization of the imide via Al-N interactions was prevented by employing the hydride [(Me3Si)2HC]2AlH 6bearing the bulky bis(trimethylsilyl)methyl substituents. Its reaction with benzonitrile yielded the compound R2Al-N=C(C6H5)H(N≡C-C6H5) 7[R = CH(SiMe3)2], in which the coordinative saturation of the aluminum atoms was achieved by adduct formation with one molecule of the starting nitrile. In these cases the C≡N triple bond inserted completely into the Al-H bond of the hydride. In contrast, the reaction of tert-butyl isonitrile afforded the product tBu2Al-C(H)=NC6H58by the insertion of its terminal carbon atom into the Al-H bond. Hence, it has a geminal arrangement of the aluminum and hydrogen atoms. Dimerization of 8yielded a six-membered heterocycle. Hydroalumination does not occur upon treatment of the hydride 1with trimethylsilylnitrile. Instead, the Si-CN bond was cleaved, and the aluminum cyanide (tBu2Al-C≡N)49was isolated in a high yield.

Journal

Zeitschrift für Naturforschung Bde Gruyter

Published: Dec 1, 2004

Keywords: Aluminum; Hydroalumination; Nitriles; Isonitriles

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