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
Permalink
