New Rhodium(I) and Iridium(I) Complexes Containing Mixed Pyrazolyl-1,2,3-Triazolyl Ligands As Catalysts for Hydroamination

作者：Hua Carol; Vuong Khuong Q; Bhadbhade Mohan; Messerle Barbara A^*

来源：Organometallics, 2012, 31(5): 1790-1800.

DOI：10.1021/om201171b

Two new bidentate pyrazolyl-triazolyl donor ligands, 44(1H-pyrazol-1-yOmethyl)-1-benzyl-1H-1,2,3-triazole, PyT (1a), and 44(1H-pyrazol-1-yOmethyl)-1-phenyl-1 H-1,2,3-triazole, PyS (1b), were synthesized using the copper(I)-catalyzed %26quot;click%26quot; reaction between 1-propargylpyrazole and benzyl azide or phenyl azide, respectively. Cationic rhodium(I) and iridium(I) complexes containing the new N-N%26apos; ligands of the general formulas [M(N-N%26apos;)(COD)]X (M = Rh or Ir, N-N%26apos; = PyT or PyS, and X = BPh4 - or BAr4F- (tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) 2a-c for Rh and 3a-c for Ir) and [M(N-N%26apos;)(CO)(2))X (M = Rh or Ir, N-N%26apos; = PyT or PyS, and X = BPh4- - or BAr4F- 4a-d for Rh and 5a-d for Ir) were successfully prepared and fully characterized. The solid-state structures of eight of these complexes were determined using single-crystal X-ray diffraction and show that the triazolyl moiety coordinates to the metal center via the N3%26apos; atom, forming six-membered metallacycles. These metallacydes- adopted a distorted boat conformation in all of the structures determined. The M-N(triazole) bonds were found to be slightly shorter than the M-N(pyrazole) bonds, illustrating the stronger donating capacity of the triazolyl donor in comparison to that of the pyrazolyl donor. All of the cationic rhodium and iridium complexes reported here are catalytically active for the intramolecular hydroamination of 4-pentyn-1-amine (6) to 2-methyl-1-pyrroline (7) at 60 degrees C, with TOFs %26gt; 400 h(-1) in many cases. The dicarbonyl complexes [M(N-N%26apos;)(CO)(2)]BAr4F (M = Rh or Ir) 4c,d and 5c,d were efficient as catalysts for the intramolecular cyclization of nonterminal allcynamines (8a,b) to cyclic imines (9a,b) via the hydroamination reaction and the cyclization of alkenamines (10a-c) to their corresponding cyclic amines (11a-c) also via the hydroamination reaction.

• 出版日期2012-3-12