1606-08-2Relevant articles and documents
Feldman et al.
, p. 1032 (1949)
Rhenium complexes of di-2-pyridyl ketone, 2-benzoylpyridine and 2-hydroxybenzophenone: A structural and theoretical study
Yumata,Habarurema,Mukiza,Gerber,Hosten,Taherkhani,Nahali
, p. 89 - 103 (2013/10/22)
The reactions of di-2-pyridyl ketone (dpk), 2-benzoylpyridine (zpy) and 2-hydroxybenzophenone (Hbp) with [Re(CO)5Cl] (A) and trans-[ReOX 3(PPh3)2] (B, X = Cl, Br) were studied. The complexfac-[Re(CO)3 (dpk·OCH3)] was isolated from the reaction of A with dpk in methanol. The monoanionic tridentate chelate dpk·OCH3 was formed by the nucleophilic attack of methanol at the carbonylic carbon atom of dpk. A similar attack of water on dpk was observed in the compound cis-[ReOBr2(dpk·OH)]·2(dpkH +Br), which was formed from dpk and [ReOBr3(PPh 3)2] in acetone. The reaction of zpy with B in acetonitrile produced the complexes [ReIIIX3(zpy)(PPh 3)], but in methanol as solvent the compounds [ReOX 2(zpyH)(PPh3)] were isolated, where zpyH coordinates bidentately as the monoanionic ligand [C6H5(HC-O)C 5H4N]. With A as starting material the complexfac-[Re(CO)3(zpy)Cl] was isolated. The complexes cis-[ReOX2(bp)(PPh3)] were the products of the reaction of Hbp with B in acetonitrile; however, in methanol cis-[ReIIIBr 2 (bp)(PPh3)2] was isolated. All these complexes were characterized by conductance measurements, elemental analyses, UV-Vis, IR and NMR spectroscopy and by single crystal X-ray diffraction. DFT calculations regarding the electronic ground states show single states for all the complexes, except for the rhe-nium(III) complexes [ReIIIX 3(zpy)(PPh3)] and [ReBr2(bp)(PPh 3)2], in which the states are triplet. The DFT and experimental results are in agreement in all cases, especially the anisotropy of the Re-N bond length offac-[Re(CO)3(dpk·OCH3)] and exact O(1)-Re-O(3) angles for [ReOX2(bp)(PPh3)].
UNIMOLECULAR H2 ELIMINATION DURING THE LIQUID PHASE RADIOLYSIS AND PHOTOLYSIS OF ALKANE-ALKANE MIXTURES
Wojnarovits, L.,Foeldiak, G.
, p. 27 - 38 (2007/10/02)
Unimolecular H2 elimination from alkanes was investigated in cyclopentane-cyclohexane, n-hexane-cyclohexane and cyclohexane-cyclooctane mixtures during radiolysis and 7.6 eV photolysis.During the radiolysis of all system, and when the fluorescence shift law allowed it, during the photolysis as well, inhibited H2 detachment was observed from the first component and sensitized hydrogen molecule elimination from the second.It has been concluded that the same excited state (the lowest singlet, S1) is responsible for the H2 elimination during radiolysis and photolysis and this is that one that gives rise to fluorescence in the experiments of other authors.The H2 and H elimination from alkanes generally have different excited precursors.The direct population of S1 by γ-irradiation is of limited importance and this intermediate is mainly produced in "charge neutralization" processes.
