Synthesis and reactivity of half-sandwich (η5-C5Me5)Ir(III) complexes of a cyclometallated aryl phosphine ligand

阅读量：

作者：

展开

摘要：

Reaction of the Ir(iii) dimer [(η5-C5Me5)IrCl2]2with PMeXyl2(Xyl = 2,6-C6H3Me2), in the presence of the poorly coordinating base 2,2,6,6-tetramethyl piperidine, gives a chloride complex1-Cl, resulting from hydrogen chloride elimination involving one of the phosphine benzylic hydrogen atoms and concomitant cyclometallation. Related compounds containing other halide or pseudohalide ligands,1-Br,1-Cl,1-SCN, can be made, the latter featuring S-coordination of the ambidentate thiocyanate to the soft Ir(iii) Lewis acid centre, as suggested by IR data and demonstrated by X-ray crystallography. Hydride2-H, and alkyl derivatives3(Me) and4(CH2SiMe3) can also be prepared from1-Cland appropriate hydride and alkylating reagents. An interesting H/D exchange chemistry that occurs in the presence of CD3OD has been disclosed for1-Cl,1-Brand2-H. For the halide derivatives, deuterium incorporation takes place into the methylene and methyl sites of their cyclometallated ligand, whereas for2-Honly the hydride and methylene (Ir–CH2) protons participate in the exchange, which is strikingly accelerated by catalytic amounts of acids.

展开

关键词：

Dye-sensitized solar cell Nanostructure Nanoparticles Nanowires Aggregates Light scattering

DOI：

10.1039/c1nj20244h

被引量：

年份：

2011