Isolation and characterisation of both the first fluoroxyfluorofullerene C60F17OF and oxahomofluorofullerenol C60F17O.OH

The first fluoroxyfluorofullerene C60F17OF (A) has been isolated from the fluorination of [60]fullerene with a mixture of MnF3 and K2NiF6 at 480ºC. This compound has a shorter HPLC retention time than the isomeric fluorofullerene ethers (oxahomofullerenes) and is less stable towards El mass spectrometry. It fragments by losing OF as a single entity and shows no formation of C60O as a fragment ion. By contrast, the ethers fragment by first losing a number of F atoms and then CO, and ultimately show also the presence of C60O, whilst epoxides lose CO as a main fragmentation step and do not give C60O. The first oxahomofluorofullerenol C60F17O.OH (B) has been isolated from the UV-irradiation of a toluene solution of C60F18 in air during 65 It and readily eliminates HF due to adjacent F and OH groups during El mass spectrometry. The structures of both the compounds have been deduced from I D and 2D 19F NMR spectroscopy. Just as oxygen inserts into FC-CF bonds of C60F18 to give ethers, so insertion into a C-F bond gives A. The oxahomofluorofullerenol B is produced by SN2' substitution of F by OH, followed by oxygen insertion into a 6:5-bond (αβ to the OH group) giving a motif not seen previously in fluorofullerenes

Novel addition in trifluoromethylation of 70 fullerene

Pyrolytic trifluoromethylation of [70]fullerene with CF3CO2Ag at 300 degreesC results in the addition of up to 12 CF3 groups to the fullerene cage. Forty-six C-70(CF3)(n) derivatives (numbers in parentheses) were separated by two-stage high pressure liquid chromatography (HPLC) as follows: n = 2(2), 4(16), 6(9), 8(14) 10(5), some being characterised by F-19 NMR. The range of derivatives is much greater than for other [70]fullerene reactions, and as with [60] fullerene trifluoromethylation, no single derivative is dominant, indicating that kinetic stability mainly controls product formation. F-19 NMR spectra show most derivatives to be unsymmetrical, with combinations of quartets and septets (overlapping quartets) due to contiguous ('linear') addend arrays, having significantly different coupling constants of the 'terminal' quartets of between 9.1 and 17.7 Hz. These differences, together with those observed previously in trifluoromethylation of [60]fullerene are consistent with addition across both 6:6- and 5:6-ring junctions. Of the two C-70(CF3)(2) isomers, one has either C-s or C-2 symmetry, the other has C-1 symmetry, whilst the C-70(CF3)(4) derivatives fall into four categories: (i) symmetrical compounds (one gives only two singlets in the F-19 NMR); (ii) unsymmetrical compounds that show a 'linear' coupling sequence; (iii) unsymmetrical compounds having a remote pairs of adjacent groups; (iv) compounds having a coupled array of three CF3 groups, together with a remote group suggesting sterically-driven migration. The first evaluation of differential NMR couplings across 6:6- and 5:6-bonds in a fullerene has been made using C60F6 as a model

Carbon-carbon Coupling On Tetrahedral Iridium Clusters: X-ray Molecular Structures And Multinuclear Nmr Studies Of The Two Isomeric Forms Of [ir4(co)6(μ3-η2 -hccph)(μ2-η4-c4h2 Ph2)(μ-pph2)2]

The reactions of [HIr4(CO)9 (Ph2PC ≡CPh)(μ-PPh2)] (1) or [Ir4(CO) 8 (μ3-η2-HCCPh) (μ-PPh2)2] (2) with HC ≡ CPh gave two isomeric forms of [Ir4(CO)6 (μ3-η2HCCPh)(μ2 -η4-C4H2Ph2) (μ-PPh2)2] (3 and 4) in good yields as the only products. These compounds were characterized with analytical and spectroscopic data including 1H, 13C and 31P NMR (1 and 2D) spectroscopy and their molecular structures were established by X-ray diffraction studies. Compounds 3 and 4 exhibit the same distorted butterfly metal polyhedral arrangement of metal atoms with two μ-PPh2 that occupy different positions in the structures of the two isomers. Both molecules contain a HCCPh ligand bonded in a μ3 -η2-// mode to one of the wings of the butterfly and a metallacyclic ring, which resulted from head-to-tail coupling, in the case of [Ir4(CO)6 (μ3-η2-HCCPh){μ-η4 -(H)CC(Ph)C(H)C(Ph)}(μ-PPh2)2] (3) and tail-to-tail coupling, in that of [Ir4(CO)6 (μ3-η2-HCCPh){μ2 -η4-(H)CC(Ph)C(Ph)C(H)}(μ-PPh2) 2] (4), and which is linked to two metal atoms of the second wing of the butterfly. © Elsevier B.V. All rights reserved.6892235133519Sappa, E., Tiripicchio, A., Braunstein, P., (1983) Chem. Rev., 83, p. 203Raithby, P.R., Rosales, M.J., (1985) Adv. Inorg. Chem. Radiochem., 29, p. 169Mallors, R.L., Blake, A.J., Dyson, P.J., Johnson, B.F.G., Parsons, S., (1997) Organometallics, 16, p. 1668Sappa, E., (1994) J. Cluster Sci., 5, p. 211. , and references thereinCarty, A.J., (1982) Pure Appl. Chem., 54, p. 113Choualeb, A., Braunstein, P., Rose, J., Welter, R., (2004) Inorg. 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Formation of Novel Sulfur-Containing C60F16 Cycloadducts between Tetrathiafulvalene and C60F18; A Unique Six-Electron Cycloaddition of a Fullerene Involving F2 Loss

Co-evaporation of solutions of C60F18 and tetrathiafulvalene in toluene produces an unsymmetrical C60F16:tetrathiafulvalene adduct through a unique six-electron cycloaddition involving displacement of two fluorine atoms by a terminal CC double bond of the fulvalene.T he adduct rearranges into two further adducts, one of which is characterised as a new type of fullerene derivative, a thiiranofullerene, formed by elimination of a thioketene moiety from the tetrathiafulvalene adduct.T he initial addition also produces a bisadduct in which the addends comprise one tetrathiafulvalene molecule and one in which carbon disulfide has been eliminated. T he latter adduct involves cycloaddition of an unsaturated aromatic dithiolactone moiety

CHO expression of a novel human recombinant IgG1 anti-RhD antibody isolated by phage display

Replacement of the hyperimmune anti-Rhesus (Rh) D immunoglobulin, currently used to prevent haemolytic disease of the newborn, by fully recombinant human anti-RhD antibodies would solve the current logistic problems associated with supply and demand. The combination of phage display repertoire cloning with precise selection procedures enables isolation of specific genes that can then be inserted into mammalian expression systems allowing production of large quantities of recombinant human proteins. With the aim of selecting high-affinity anti-RhD antibodies, two human Fab libraries were constructed from a hyperimmune donor. Use of a new phage panning procedure involving bromelin-treated red blood cells enabled the isolation of two high-affinity Fab-expressing phage clones. LD-6-3 and LD-6-33, specific for RhD. These showed a novel reaction pattern by recognizing the D variants D(III), D(IVa), D(IVb), D(Va), D(VI) types I and II. D(VII), Rh33 and DFR. Full-length immunoglobulin molecules were constructed by cloning the variable regions into expression vectors containing genomic DNA encoding the immunoglobulin constant regions. We describe the first, stable, suspension growth-adapted Chinese hamster ovary (CHO) cell line producing a high affinity recombinant human IgG1 anti-RhD antibody adapted to pilot-scale production. Evaluation of the Fc region of this recombinant antibody by either chemiluminescence or antibody-dependent cell cytotoxicity (ADCC) assays demonstrated macrophage activation and lysis of red blood cells by human lymphocytes. A consistent source of recombinant human anti-RhD immunoglobulin produced by CHO cells is expected to meet the stringent safety and regulatory requirements for prophylactic application