Dimerisation of alpha-olefins by a catalyst system comprising of a bis(imido) tungsten compound and a Lewis acid component has been investigated by density functional theory employing a catalyst model that closely mimics the real system together with ethylene chosen as a prototypical substrate. This study disclosed that the Lewis acid preferably forms four-membered chelates by bridging across t...

Unprecedented imido phthalocyaninato complexes of pentavalent refractory metals [PcM(NR)Cl] (M = Mo, W, Re; R = tBu: 1, 3, 6, Mes: 2, 4, 7 or Ts: 5) have been synthesized by reductive cyclotetramerization of phthalonitrile in the presence of appropriate bis(imido) complexes of Mo, W and Re as templates. While d(1) Mo(V) and W(V) species 1-5 show distinctive EPR spectra corresponding to metal ce...

The synthesis and characterization of uranium(VI) mono(imido) complexes, by the oxidation of corresponding uranium(V) species, are presented. These experimental results, paired with DFT analyses, allow for the comparison of the electronic structure of uranium(VI) mono(oxo) and mono(imido) ligands within a conserved ligand framework and demonstrate that the magnitude of the ground state stabiliz...

{Bo(M)Cp(tet)}Lu(CH2Ph)2 (1; Bo(M)Cp(tet) = MeC(Ox(Me2))2C5Me4; Ox(Me2) = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of Bo(M)Cp(tet)H and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{Bo(M)Cp(tet)}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {Bo(M)Cp(tet)}Lu(NHCH2R)2 (R = C6...

In the neutral title compound, [Re(C(6)H(5)NO)(C(13)H(9)NO(2))(CH(3)O)(C(18)H(15)P)], an 18-valence-electron complex, the Re(V) ion lies in an octa-hedral coordination geometry with the tridentate dianionic Schiff base 2-(2-oxidobenzyl-idene-amino)phenolate ligand occupying three equatorial coordination sites, and with the triphenyl-phosphine ligand situated trans to the imine N atom. The Re(V)...

The zirconium and hafnium imido metalloporphyrin complexes (TTP)M = NArtPr (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; AriPr = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products ...

In this paper we use first principles quantum mechanical methods (B3LYP flavor of density functional theory) to examine the mechanism of selective oxidation and ammoxidation of propene by BiMoOx catalysts. To do this we use finite clusters chosen to mimic likely sites on the heterogeneous surfaces of the catalysts. We conclude that activation of the propene requires a Bi(V) site while all subse...

In this paper, we use first principles quantum mechanical methods (B3LYP flavor of Density Functional Theory) to examine the mechanism of selective oxidation and ammoxidation of propene by BiMoOx catalysts. To do this, we use finite clusters chosen to mimic likely sites on the heterogeneous surfaces of the catalysts. We conclude that activation of the propene requires a Bi(V) site, whereas all ...