RESUMO
The conjugate acids (PHCH+s) of P-heterocyclic carbenes (PHCs) are prepared by formal [3+2] cycloaddition of a 1,3-diphosphaallyl or 1,3-phosphinophosphenium cation with various nitriles. The effect of the phosphorus substituent on the fate of the cyclization and on that of the counteranion and base in the subsequent deprotonation reaction are reported. Two PHCs that are indefinitely stable in the solid state are described. In solution, one of them, made from acetonitrile, undergoes a facile [3+2] cycloreversion, whereas the other, based on dimethyl cyanamide, is stable, presumably owing to its zwitterionic structure, which involves a tricoordinate pentavalent phosphorus atom. The reactivity of PHCs is strongly driven by the high electrophilicity of the phosphorus centers, as demonstrated by their reactivity with water and benzaldehyde. Although both PHCs reported in this paper are direct analogues of the least-basic NHCs, their basicity is comparable to those of the more strongly basic NHCs (as determined by comparison of the carbonyl stretching frequencies of their corresponding cis-[RhCl-(CO)2(L)] complexes).
Assuntos
Compostos Heterocíclicos/síntese química , Metano/análogos & derivados , Catálise , Cristalografia por Raios X , Compostos Heterocíclicos/química , Hidrocarbonetos/química , Metano/química , Modelos Moleculares , Estrutura Molecular , Fosfinas/químicaRESUMO
Two original complexes featuring an (amino)(phosphino)carbene η(2)-bonded to the metal have been obtained in 60 and 80 % yields, by addition of the corresponding stable carbene to PdCl(2)(cod) and NiCl(2)(PPh(3))(2), respectively. Both complexes have been fully characterized including X-ray diffraction studies. The catalytic activity of the palladium complex has been evaluated for aryl amination reactions.
