Diamino- and Mixed Amino-Amido-N-Heterocyclic Carbenes Based on Triazine Backbones

作者：Makhloufi Abdelaziz; Frank Walter; Ganter Christian^*

来源：Organometallics, 2012, 31(5): 2001-2008.

DOI：10.1021/om201275z

The synthesis of novel hexahydrotriazine-based NHCs from easily available starting materials is described. Tribenzyltriazacyclohexane 1 is converted stepwise to the six-membered diamino carbene 3 with a saturated ring structure. Analogously, the cyclic mixed amino-amido carbene 12 is obtained starting from a cyclic urea derivative. Both carbenes were characterized by trapping reactions with sulfur and selenium as well by the preparation of metal complexes of the type (COD)MX-NHC (M = Rh; Ir; COD = 1,5-cyclooctadiene), which were converted to the respective dicarbonyl complexes (CO)(2)MX-NHC. IR spectra of the carbonyl derivatives allowed the Tolman electronic parameter to be determined for carbenes 3 (2052 cm(-1)) and 12 (2058 cm(-1)) and revealed a shift of 6 cm(-1) due to the presence of one amide function. X-ray structure detenninations are reported for an amidinium species, a carbene sulfide, and the (COD)RhBr complex of the amino amid carbene 12.

• 出版日期2012-3-12