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首页> 美国政府科技报告 >Synthesis and reactions of thiophene, 2,5-dihydrothiophene, Benzo(b)thiophene and seleophene transition metal complexes: Models for catalytic hydrodesulfurization.
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Synthesis and reactions of thiophene, 2,5-dihydrothiophene, Benzo(b)thiophene and seleophene transition metal complexes: Models for catalytic hydrodesulfurization.

机译：噻吩，2,5-二氢噻吩，苯并（b）噻吩和硒吩过渡金属配合物的合成和反应：催化加氢脱硫的模型。

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S-coordinated thiophene (Th) complexes Cp(prime)(CO)(sub 2)Re(Th), Cp(prime) = Cp or Cp* and Th = T, 2-MeT, 3-MeT, 2,5-Me(sub 2)T, Me(sub 4)T and dibenzothiophene (DBT), have been synthesized. The compounds Cp(prime)(CO)(sub 2)Re(Th) (Th = T, 2-MeT and 3-MeT) react with Fe(sub 2)(CO)(sub 9) to give thiophene-bridged dinuclear complexes Cp(prime)(CO)(sub 2)Re((mu)(sub 2)-(eta)(sup 4)(S)-Th)Fe(CO)(sub 3). The first X-ray structures of a simple nonchelated S-bound thiophene complex Cp*(CO)(sub 2)Re(T) and a thiophene-bridged compound Cp*(CO)(sub 2)Re((mu)(sub 2)-(eta)(sup 4)(S)-T)Fe(CO)(sub 3) are also report. Several S-coordinated 2,5-dihydrothiophene (2,5-DHT) transition metal complexes were synthesized to investigate the possibility of metal promoted butadiene formation as proposed in a HDS mechanism. Thermal decomposition of W(CO)(sub 5)(2,5-DHT) and Re(sub 2)(CO)(sub 9)(2,5-DHT) at 110(degree)C liberate the butadiene and free 2,5-DHT (relative ratio 1:4). The benzo(b)thiophene complexes Cp(prime)(CO)(sub 2)Re(BT) exist as S- and 2,3-(eta)(sup 2)-bound BT isomers in rapid equilibrium with each other. Replacing Cp by Cp* shifts the equilibrium in favor of the (eta)(sup 2)-isomer. A structural determination of Cp*(CO)(sub 2)Re(2,3-(eta)(sup 2)-BT) confirms this new bonding mode. In the Se analogs of thiophene complexes, Cp*(CO)(sub 2)Re(Sel), the selenophene (Sel) coordinates to Re through Se or (eta)2 through the olefin depending of the number of methyl groups on the selenophene ring. The structure of Cp*(CO)(sub 2)Re((mu)(sub 2)-(eta)(sup 4)(Se)-Sel)W(CO)(sub 4)(PPh(sub 3)) is reported. These studies and the discovery of several novel bonding modes ((eta)(sup 2)-BT, (mu)(sub 2)-(eta)(sup 4)(S)-Th, and (mu)(sub 2)-(eta)(sup 2)(Se)-Sel) suggest possible new modes of thiophene adsorption and activation in HDS catalysis. 13 refs., 4 figs., 16 tabs.

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