Indium(II1) iodide forms both 1: 1 and 1 :2 adducts with triphenylphosphine, depending on the reaction conditions, and especially on the solvent used. The complex In13.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 ~3 .Crystals were also obtained in which In13. PPh3 and In13(PPh3), 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 ~3 .The 1:2 adduct has approximately D3,, symmetry in the In13P2 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 3 1~ NMR to undergo complete dissociation in solution to In13.PPh3 and PPh,. The addition of R4NI (R = n-C3H7, n-C4Hg) causes quantitative conversion to Id4-and free Ph,P. Similar experiments are reported for the compound In13(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane), whose structure is an infinite chain of InI, units linked through In-P-C2H4-P-In coordination. The crystal structure showed that InI,(dppe) cocrystallizes with an equimolar quantity of dppe; these crystals are cubic, a = 41.445 (14)

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The solid state structures of the compounds GaI3•PPh3 and Ga2I6•dppe ( dppe = 1,2-bis(diphenylphosphino)ethane ) have been determined. For the former, in which the GaI3P core has C3v symmetry, the structure is trigonal, with a = 14.961(2) Å, c = 16.509(3) Å, V = 3199.5(4) Å3, Z = 6, space group [Formula: see text]. In Ga2I6•dppe, the ligand bridges two GaI3P centres; the structure is monoclinic, a = 10.196(7) Å, b = 15.363(1) Å, c = 23.027(9) Å, β = 98.735(4)°, V = 3565.1(3.2) Å3Z = 4, space group P21/n The use of 31P NMR spectroscopy shows that GaI3•PPh3 is slightly dissociated in nonaqueous solution, and the effect of adding Ph3P or I− has been investigated. Similar studies with Ga2I6•dppe are also reported. In each system, four-coordination at gallium is dominant; an equally important factor is the dimerization of uncomplexed GaI3 to Ga2I6 in these solutions. Keywords: gallium(III) iodide, complexes, phosphorus, NMR, crystallography.

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Experiments were undertaken to isolate a component of the serum of goat (Capra hircus) that is effective at mediating an innate immune response. This report describes the isolation and structure elucidation of 1-(N-acetyl-ALYDKGYTSKEQKDCVGI)-2-arachidonoyl-3-stearoyl glyceride (1) and its immunomodulatory activity. A dose-response relationship for inflammatory cytokine and chemokine production and release from human fibroblasts incubated with nanomolar concentrations of 1 was shown. Moreover, the membrane transport role of the diacylglycerol moiety in 1 is demonstrated with nanomolar quantities of the transfected N-acetyl peptide moiety of 1 also inducing inflammatory cytokine and chemokine production and release. The apparent EC99 for 1 was 3 ng/mL (1 nM). The likely biological role for naturally occurring 1 as a damage-associated molecular pattern is postulated.

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Indium(II) iodide reacts with various substituted o-quinones in nonaqueous solution by successive one-electron-transfer reactions to give (SQ)InI(2) 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 In(2)I(4) and TBQ (=3,5-di-tert-butyl-o-quinone) in toluene causes the precipitation of the indium(III)-semiquinonate complex (TBSQ)InI(2)(pic)(2) whose structure has been established by X-ray crystallography: space group P&onemacr;, with a = 13.013(3) Å, b = 13.317(3) Å, c = 10.828(5) Å, alpha = 97.71(3) degrees, beta = 107.98(3) degrees, gamma = 103.92(3) degrees, V = 1684.8(1.2) Å(3), Z = 2. Refinement converged at R = 0.051 and R(w) = 0.064 for 5918 reflections at 23 degrees C. The InO(2)N(2)I(2) kernel is pseudooctahedral, and the structure confirms the presence of the semiquinonate ligand. A reaction scheme which incorporates these results is proposed.