15810-57-8Relevant academic research and scientific papers
Spectroscopic and crystallographic studies of phosphino adducts of indium(III) iodide
Brown, Martyn A.,Tuck, Dennis G.,Wells, Edward J.
, p. 1535 - 1549 (1996)
Indium(III) iodide forms both 1:1 and 1:2 adducts with triphenylphosphine, depending on the reaction conditions, and especially on the solvent used. The complex InI3·PPh3 involves four-coordination at indium; the structure is trigonal, with a = 15.105(4) A, c = 16.769(7) A, V = 3313(2) A3, Z = 6, and space group R3. Crystals were also obtained in which InI3·PPh3 and InI3(PPh3)2 are present in a 1:1 ratio; these are also trigonal, a = 15.473(4) A, c = 41.701(7) A, V = 8646.1(1.8) A3, Z = 3 + 3 and space group R3. The 1:2 adduct has approximately D3h symmetry in the InI3P2 kernel. The bond distances and angles are discussed; in particular, the In-P bonds are extremely weak in the 1:2 adduct. This compound has been shown by 31P NMR to undergo complete dissociation in solution to InI3·PPh3 and PPh3. The addition of R4NI (R = n-C3H7, n-C4H9) causes quantitative conversion to InI4- and free Ph3P. Similar experiments are reported for the compound InI3(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane), whose structure is an infinite chain of InI3 units linked through In-P-C2H4-P-In coordination. The crystal structure showed that InI3(dppe) cocrystallizes with an equimolar quantity of dppe; these crystals are cubic, a = 41.445(14) A, b = 15.944(8) A, c = 16.533(11) A, β = 102.02(4)°, V = 10 685(9) A3, Z = 4 + 4, space group C2/c. Solid state and solution phase results are discussed in terms of the coordination chemistry of indium(III).
Electron-Transfer Processes in Indium(II) Iodide-o-Quinone Systems
Brown, Martyn A.,McGarvey, Bruce R.,Ozarowski, Andrzej,Tuck, Dennis G.
, p. 1560 - 1563 (1996)
Indium(II) iodide reacts with various substituted o-quinones in nonaqueous solution by successive one-electrontransfer reactions to give (SQ)InI2 products (SQ = semiquinonate radical anion). Electron spin resonance spectroscopy demonstrates the presence of both mono- and diradical species in the reaction mixture. Addition of 4-picoline to a mixture of In2L4 and TBQ (=3,5-di-tert-butyl-o-quinone) in toluene causes the precipitation of the indium(III)-semiquinonate complex (TBSQ)InI2(pic)2 whose structure has been established by X-ray crystallography: space group P1?, with a = 13.013(3) ?, b = 13.317(3) ?, c = 10.828(5) ?, α = 97.71(3)°, β= 107.98(3)°, y = 103.92(3)°, V = 1684.8(1.2) ?3, Z = 2. Refinement converged at R = 0.051 and Rw = 0.064 for 5918 reflections at 23 °C. The InO2N2I2 kernel is pseudooctahedral, and the structure confirms the presence of the semiquinonate ligand. A reaction scheme which incorporates these results is proposed.
Adducts of GaI3 and InI3 with Ph3P and Ph3As
Baker,Kloo, Lars A.,Rickard, Clifton E.F.,Taylor, Michael J.
, p. 249 - 255 (2007/10/03)
Adducts Ph3PGaI3 and Ph3AsGaI3 obtained by adding the ligands to Et2OGaI3 have been investigated by 71Ga NMR, IR/Raman spectroscopy and X-ray diffraction, Et2OInI3 with Ph3P gives (Ph3P)3(InI3)2. Ph3As yields (Ph3As)3(InI3)2 · H2O as rhombohedral crystals whose structure was solved by X-ray diffraction. Both these indium complexes contain Ph3EInI3 molecules alongside five-coordinate aclducts (Ph3E)2InI3 with the Ph3E ligands attached in axial sites by long and unequal bonds to a planar InI3 unit. Vibrational assignments are made for Ph3PGaI3, Ph3AsGaI3, Ph3EInI3 and (Ph3E)2InI3 (E = P or As).
