101075-58-5Relevant articles and documents
Mimicking the HDS activity of promoted tungsten catalysts. A homogeneous modeling study using a two-component tungsten/rhodium system
Bianchini, Claudio,Jiménez, M. Victoria,Meli, Andrea,Moneti, Simonetta,Patinec, Véronique,Vizza, Francesco
, p. 5696 - 5705 (2008/10/08)
Reaction of W(CO)5THF with (triphos)Rh[η3-S(C6H4)CH=CH2] (1), obtained by insertion of the 16e- fragment [(triphos)RhH] into the C2-S bond of benzo[b]thiophene (BT), gives the dimer (triphos)Rh[η3-(CO)5WS(C6H 4)CH=CH2] (2; triphos = MeC(CH2PPh2)3). Unlike 1, the heterometal dimer 2 reacts with H2 (30 atm) above 70°C in THF, undergoing the desulfurization of the C-S-inserted BT. As a result, a mixture of the hydrido carbonyl species (triphos)RhH(CO), ethylbenzene, and WSx (xav = 1.5) is obtained. High-pressure NMR spectroscopy in the temperature range from 20 to 70°C shows that the desulfurization step is preceded by the formation by the dimer (triphos)RhH(μ-H)[μ-o-S(C6H4)C2H 5]W(CO)4 (5), in which the Rh and W centers are held together by bridging 2-ethylthiophenolate and hydride ligands. Complex 5 has been characterized in both the solid state (single-crystal X-ray analysis) and solution (multinuclear NMR spectroscopy). The desulfurization of 5 occurs also by thermolysis in THF at 120°C under a nitrogen atmosphere. Reaction of 5 with CO (30 atm, 40°C) gives the complex [(triphos)Rh(CO)2][(CO)5W(o-S(C6H 4)C2H5)] (8), in which the thiolate ligand is η1-S bound to the tungsten atom in the complex anion [(CO)5W-(o-S(C6H4)C2H 5)]-. The hydrogenation of 8 (30 atm of H2, > 70°C) gives exclusively free 2-ethylthiophenol. The carbonylation of 2 (30 atm of CO, room temperature) results in the formation of [(triphos)Rh(CO)2][(CO)5W(o-S(C6H 4)CH=CH2)] (3), in which the 2-vinylthiophenolate ligand is η1-S bound to the tungsten atom. The possible similarity in the C-S bond cleavage mechanism in the desulfurization of 5 to those occurring in the HDS over promoted heterogeneous catalysts is discussed.
SOME RHODIUM(I) AND RHODIUM(III) COMPLEXES WITH THE TRIPOD-LIKE LIGANDS RC(CH2PPh2)3 (R=Me: triphos; R=Et: triphos-I) AND THE X-RAY CRYSTAL STRUCTURE OF
Ott, J.,Venanzi, L. M.,Ghilardi, C. A.,Midollini, S.,Orlandini, A.
, p. 89 - 100 (2007/10/02)
The syntheses of (8, triphos=CH3C(CH2PPh2)3) and the related compound (triphos-I=EtC(CH2PPh2)3) are described, and the X-ray crystal structure of the latter is reported.The crystals are monoclinic space group P21/a, a 15.985(6), b 19.683(7), c 11.900(4) Angstroem, β 103,73(6) degree, Z=4.The structure was solved by the heavy atom method and refined by full-matrix leastsquares to the conventional R factor value of 0.057 for 2649 observed reflections.The metal atom is octahedrally coordinated by three phophorus atoms and by three hydrogen atoms, each trans to one phosphorus.Complex 8 has been shown to react with CO to give (2).Compound 2 reacts with CH2=CHCO2Me to give only the branched insertion product .The complex has been re-investigated and was obtained in a single isomeric form which has been assigned a five-coordinate structure.The five-coordinate compounds (X=Br and I) are also described.
