104453-05-6Relevant articles and documents
Triphos iridium(III) halide complex photochemistry: Triphos arm dissociation
Ross, Andreas,Sharp, Paul R.
, p. 12645 - 12654 (2013/11/19)
Photolysis of Ir(triphos)X3 (triphos = 1,1,1- tris(diphenylphosphinomethyl)ethane; X = Cl, Br) yields an insoluble product believed to be oligomeric [Ir(triphos)X3]n with bridging triphos and halide ligands. Refluxing pyridine (py) dissolves the insoluble photoproducts ultimately yielding the dangling triphos complexes mer-Ir(κ2-triphos)(py)X3. Oxidation of the P center of the dangling arm of Ir(κ2-triphos)(py)Cl3 yields mer-Ir(κ2-P,P-triphosO)(py)Cl3 (triphosO = MeC(CH2P(O)Ph2)(CH2PPh2) 2), which was characterized by single-crystal X-ray diffraction. mer-Ir(κ2-triphos)(py)Cl3 is also formed when Ir(triphos)Cl3 is photolyzed in the presence of py (φ = 26%). Both mer-Ir(κ2-triphos)(py)Cl3 and mer-Ir(κ2-P,P-triphosO)(py)Cl3 photoisomerize in pyridine to their thermally unstable fac-isomers. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations suggest triphos ligand arm dissociation occurs along a triplet pathway from an initial Franck-Condon ligand-field excited state that relaxes to a Jahn-Teller axially distorted octahedral triplet with a long Ir-P bond. Subsequent triphos arm dissociation yields a distorted trigonal-bipyramidal triplet that undergoes intersystem crossing to a square pyramidal singlet.
SOME IRIDIUM(I) AND IRIDIUM(III) COMPLEXES WITH THE TRIPOD-LIKE LIGAND CH3C(CH2PPh2)3 (triphos) AND THE X-RAY CRYSTAL STRUCTURE OF
Janser, P.,Venanzi, L. M.,Bachechi, F.
, p. 229 - 242 (2007/10/02)
The compound (1), has been reinvestigated and its X-ray crystal structure is reported.The crystals are orthorhombic, space group Pbca, with a 18.941(6), b 22.193(8), c 17.501(7) Angstroem, Z = 8.The structure was solved by the heavy atom method and refined by full-matrix least-squares to the conventional R factor value of 0.074 for 6462 reflections.The metal atom coordination is trigonal bipyramidal, with the three phosphorus atoms occupying one axial and two equatorial positions.The other equatorial position is occupied by CO while Cl is coordinated axially.Compound 1 readily undergoes a series of oxidative-addition reactions with H2, HCl and Cl2, giving + (4) + (3), and (IrCl3(triphos)> (5), respectively.Compounds (IrH(CO)(triphos)> (2) and nCl3-n(triphos)> (n = 1,2,3) have also been obtained from 1 and 5, respectively, by treating them with a variety of hydride sources.