Synthesis and characterisation of PCsp3P phosphine and phosphinite iridium complexes. Cyclometallation and dehydrogenation of a cyclohexyl ring.
A cyclohexyl based pincer phosphine ligand undergoes cyclometalation with an iridium cyclooctadiene precursor to give a highly thermally stable iridium(III) complex where a C(sp3)-H bond has been oxidatively added. This iridium(III) hydride complex is reduced with potassium to give a terminal iridium(I) dinitrogen complex with no tendency to dimerization. The corresponding cyclohexyl phosphinite ligand undergoes reversible dehydrogenation to give the aromatic cyclometalated iridium(III) hydride complex together with 3 equivalents of dihydrogen.
Arunachalampillai
Athimoolam
A
Organic Chemistry, Department of Chemistry, Lund University, P.O. Box 124, S-221 00, Lund, Sweden.
Olsson
Daniel
D
Wendt
Ola F
OF
D018360:Crystallography, X-Ray; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D010721:Phosphinic Acids / Q000737:chemistry*; D013237:Stereoisomerism
D003510:Cyclohexanes; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D010721:Phosphinic Acids; D007495:Iridium; C044646:phosphine