Sergiu M. Gorun

Synthesis and structural characterization of non-planar perfluoro phthalonitriles

Abstract Perfluoropropene reacts with 1,2-dicyano-3,4,5,6-tetrafluorobenzene to give the first perfluoroalkyl substituted phthalonitriles. The X-ray structures of the bis- and tris-substituted products reveal planar, undistorted rings and head-to-head and head-to-tail preferred conformations for the isopropyl substituents, respectively. As a result, the CF3 groups impart global non-planar character to the new molecules.

Dome-distortion and fluorine-lined channels: synthesis, and molecular and crystal structure of a metal- and C–H bonds-free fluorophthalocyanine

The first perfluorinated metal-free phthalocyanine exhibits a dome-like molecular distortion usually induced by large metal ions. Fluorine-lined channels account for ∼ 39% of the unit cell volume. The intermolecular interlocking of peripheral iso-perfluoroalkyl short-chains contributes to these features, which could be used in the rational design of robust materials.

Synthesis and molecular structures and oxidation catalysis of mixed alkyl, fluoroalkyl pyrazolylborate metal complexes

Abstract First row transition metal complexes of partly fluorinated tris- and bispyrazolylborate complexes are synthesized and structurally characterized. Both the red cobalt complex, [{η3-HB(3-CF3-5-CH3pz)3}Co(η2-NO3)(NCCH3)] (1a) and the colorless manganese analogue, [{η3-HB(3-CF3-5-CH3pz)3}Mn(η2-NO3)(NCCH3)] (1b), exhibit a N4O2 donor set which defines a distorted octahedral geometry. For the blue–purple complex Cu[η2-H2B(3-CF3-5-CH3pz)2]2 (2), the N4 donor set defines a symmetry-imposed tetragonal geometry. The ligand(s) in 1 and 2 define relatively open and closed fluorine-lined cavities around their metal centers, respectively. The cavity of 1a and 1b allows additional facial coordination by small ions and neutral molecules such as NO3xa0− and MeCN. In contrast, the metal in 2 is in a more saturated, quasi-octahedral environment, defined by two non-bonding axial Cu⋯H contacts and the N4 donor set. Catalytic oxidation of cyclohexane using 1a and cumene hydroperoxide as oxygen donor yields a 1:1 mixture of cyclohexanol and cyclohexanone, and occurs 50% faster compared with the non-fluorinated analogous complex.

Complexes exhibiting non-conventional solubility: synthesis and characterization of trans-Pt[(CF3(CF2)5(CH2)2)3P]2Cl2 ☆

Abstract Synthetic approaches have been developed for preparing fluorocarbon solvent and liquid and supercritical CO 2 (sc CO 2 ) soluble organometallic complexes. To explore solubility in these media, the synthesis of a number of organometallic complexes containing the phosphine ligand (CF 3 (CF 2 ) 5 (CH 2 ) 2 ) 3 P 2 , is reported. The platinum(II) complex, trans -Pt[(CF 3 (CF 2 ) 5 (CH 2 ) 2 ) 3 P] 2 Cl 2 1 , has been synthesized, isolated, and characterized by X-ray crystallography and 31 P-NMR spectroscopy. Complex 1 , PtC 48 H 24 Cl 2 F 78 P 2 crystallizes in the triclinic space group P 1 , with a =11.632(2), b =16.970(2), c =20.838(3) A; α =71.67(1), β =80.22(2), γ =88.18(2)°; Z =2, and R F ( R WF 2 )=0.0789 (0.108) for 8095 reflections. The Pt coordination is trans square planar with the long fluoroalkyl chains of the (CF 3 (CF 2 ) 5 (CH 2 ) 2 ) 3 P ligands being nearly perpendicular to the coordination plane.

Activation of a Carbon–Oxygen Bond of Benzofuran by Precoordination of Manganese to the Carbocyclic Ring: A Model for Hydrodeoxygenation

Stable unsaturated heterocycles such as benzofuran are difficult to remove from petroleum by conventional catalytic hydrotreating. However, in a model system, coordination of Mn(CO)(3)(+) to the aromatic ring of benzofuran activates the C-O bond towards insertion of [Pt(PPh(3))(2)] [Eq. (1)]. The insertion is preceded by precoordination to the furan C=C bond; thus, the 2,3-dihydro analogue of 1, which lacks this double bond, does not undergo insertion of the Pt moiety.

Aktivierung einer Kohlenstoff-Sauerstoff-Bindung von Benzofuran durch Vorkoordination von Mangan an den Carbocyclus: ein Modell für die Hydrodesoxygenierung

Stabile ungesattigte Heterocyclen wie Benzofuran lassen sich kaum durch konventionelle katalytische hydrierende Behandlung aus Erdol entfernen. In einem Modellsystem jedoch aktiviert die Koordination von Mn(CO)3+ an den aromatischen Ring von Benzofuran die C-O-Bindung fur eine Insertion von [Pt(PPh3)2] [Gl. (1)]. Der Insertion geht eine Koordination des Pt-Zentrums an die Furan-C=C-Bindung voraus; in Einklang damit last sich in das 2,3-Dihydro-Analogon von 1, dem diese Doppelbindung fehlt, die Pt-Einheit nicht inserieren.

Transient grating studies of laser induced 1ΔgO2 production by photodynamic therapy agents

The transient grating method acts as a monitor of the evolution of thermal energy following optical excitation of an absorbing molecule. The signals produced by a photodynamic therapy agent are shown to be strongly dependent on presence of oxygen in solution indicating transfer of energy from a triplet state of the dye to form excited 1Δg oxygen. Analysis of the data shows that the efficiency of excited oxygen production can be determined by a recording of the diffracted light intensity versus time.