En route to phosphonato iridium(i) complexes: the decisive effect of an intramolecular hydrogen bond.

摘要: Pentacoordinated iridium(I) complexes of formula IrCl(SiNP)(tfbb) (1) and IrCl(HNP)2(tfbb) (2) (SiNP = SiMe2{N(4-C6H4CH3)PPh2}2; HNP NH(4-C6H4CH3)PPh2) have been prepared fully characterised. Both feature a distorted square pyramidal coordination polyhedron at the metal centre in solid state are fluxional solution. Their reaction with trimethyl phosphite yields derivatives [Ir(SiNP){P(OMe)3}(tfbb)]Cl ([3]Cl) Ir{PO(OMe)2}(HNP)2(tfbb) (4). The course between was elucidated by NMR spectroscopy DFT calculations, showing that intermediate [Ir(HNP)2{P(OMe)3}(tfbb)]+ (5+) forms further reacts chloride anion yielding phosphonato derivative 4 methyl chloride. decisive role N–H group formation ligand has established IR spectroscopic measurements calculations.