W. P. Fehlhammer, W. Finck
Aug 20, 1991
Citations
0
Influential Citations
17
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract μ-(1,2-Diisocyanobenzene)bis(chlorogold) (2) reacts with 1,2-diaminobenzene ( 1 2 to give benzimidazolin-2-ylidene(chloro)gold (3) as the only reaction product, while 1 1 -mixtures of 3 and the corresponding diaminocarbene complexes (4, 6) result from the reactions of 2 with 1,8-diaminonaphthalene or two equivalents of aniline. With one equivalent of a primary amine (MeNH2, PhNH2), however, the isocyanide complexes Au(C1)CNR (R = Me, Ph) are obtaained, again together with 3. Mechanistic key steps following the primary nucleophilic attack by the amine are a novel NC-coupling of the two neighbouring isocyano functions to give a benzimidazole ring system, and the transfer of the exocyclic Au(CI)C fragment onto the incoming amine. Accordingly, the reactions between 2 and secondary amines 2 and secondary amines lead to an isolable binuclear intermediate C′ ( 1 1 ) or to the carbene complexes Au(Cl){C(NR2)2} (8, 2R = (CH2)5; 9, 2R = (CH2)2O(CH2)2; 10, R = Me; 11, 2R = (CH2)4) ( 1 2 ), respectively. 7 and morpholine give 3 and the asymmetrical diaminocarbene complex Au(Cl){C[ N(CH 2 ) 4 C H2][ N(CH 2 ) 2 OCH 2 C H2] } (12).