Analysis of a hydrodesulfurization process— 2 [1]. The reactions of 2- and 3-methylthiophenes with tris(triethylphosphine)platinum(0)

Garcı́a, Juventino J.; Arévalo, Alma; Capella, Santiago; Chehata, Alexander; Hernández, María Estela Orozco; Montiel, Virginia; Picazo, Graciela; Río, Federico del; Toscano, Rubén A.; Adams, Harry; Maitlis, Peter M.

doi:10.1016/s0277-5387(97)00021-1

Cited by 35 publications

(25 citation statements)

References 23 publications

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“…We have reported several investigations of the chemistry of thiaplatinacycles derived from thiophenes and platinum(0); those thiaplatinacycles can be envisaged to result from an oxidative insertion into a thiophene C−S bond. Pt(PEt 3 ) 3 , 1 , successfully reacted with dibenzothiophene (to produce 2, Scheme ), benzothiophene, thiophenes, and methylthiophenes. , Recently we demonstrated that using other phosphines such as PMe 3 and dppe, it is possible to activate benzothiophene and 4-methyldibenzothiophene 4e to produce the corresponding thiaplatinacycles. Related thiaplatinacycles have been reported quite recently by Sweigart and co-workers, using transition-metal fragments coordinated to the π-system of thiophene, benzothiophene, and dibenzothiophene and adding Pt(PPh 3 ) 3 as nucleophile, producing a C−S cleavage.…”

Section: Introductionmentioning

confidence: 99%

Ring Opening of Methylbenzothiophenes and Methyldibenzothiophenes by Tris(triethylphosphine)platinum(0)

et al. 1999

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The reaction of [Pt(PEt3)3], 1, with 3-methylbenzothiophene and 2-methylbenzothiophene afforded the thiaplatinacycles [(Et3P)2Pt(C,S-C9H8S)], 3 and 4, respectively. In the formation of both complexes (Et3P)2Pt has inserted into the C−S bond to the vinylic carbon. Complex 4 rearranges in solution to a dimeric thiaplatinacycle, 5, in which the platinum has moved from lying between the vinylic C−S bond into the aromatic C−S bond. Reaction of 1 with 4-methyldibenzothiophene gave a mixture of isomeric thiaplatinacycles [(Et3P)2Pt(C,S-C13H10S)], 6 and 7. The reaction of 1 with 4,6-dimethyldibenzothiophene containing some 1,9-dimethyldibenzothiophene led to the isolation of complex 9, [(Et3P)2Pt(C,S-C14H12S)]. This is derived from 1,9-dimethyldibenzothiophene, which is a byproduct in the preparation of 4,6-dimethyldibenzothiophene by a metalation pathway. The reaction of 1 with highly pure 4,6-dimethyldibenzothiophene gave the hydride complex, 10, in which (Et3P)2Pt has inserted into the C−H bond at the 3-position. The thiaplatinacycle cis-[(Et3P)2Pt(η2-C,S-C14H12S)], 8, was obtained by reaction of highly pure 4,6-dimethyldibenzothiophene with cis-[PtCl2(PEt3)2] and metallic sodium under hydrogen. X-ray structures of complexes 3, 5, and 9 are reported.

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Section: Introductionmentioning

confidence: 99%

Ring Opening of Methylbenzothiophenes and Methyldibenzothiophenes by Tris(triethylphosphine)platinum(0)

et al. 1999

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“…In our researches to model such HDS reactions we have found that the platinum(0) complex [Pt(PEt 3 ) 3 ] can reversibly oxidatively insert into the C-S bonds of T, BT or DBT, giving six-membered thiaplatinacycles. [3][4][5] These thiaplatinacycles extrude S and Pt on reaction with sources of hydride to give hydrocarbons, thus demonstrating a full HDS sequence mediated by platinum.…”

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New hydrogenation and isomerization reactions involving thiaplatinacycles derived from benzothiophene

Iretskii¹,

Adams²,

Maitlis³

et al. 1998

Chem. Commun.

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“…For example, Jones has shown that reaction of the 16-electron fragment [(C 5 Me 5 )Rh(PMe 3 )] with 2-methylthiophene results in selective insertion into the less hindered, nonalkylated S−C bond . This tendency for insertion to occur away from ring substituents has been observed in a number of thiophene complexes as well as alkylated dibenzo-thiophene systems. ,− Steric interactions have also been shown to play an important role in the configuration of the ring systems in a number of metal-inserted thiophene complexes. We have reported that the distortions observed in the metallacycles of various systems can be virtually eliminated by removal or reduction of sterically demanding ligands .…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Molecular Orbital Study of Organometallic Complexes Containing Benzo[b]thiophene

1998

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Ab initio molecular orbital calculations have been carried out on benzo[b]thiophene (BT), 2-methylbenzo[b]thiophene (2-MeBT), 3-methylbenzo[b]thiophene (3-MeBT), and a number of organometallic complexes containing these thiophenic moieties in an attempt to understand the usual preference for insertion of metal fragments into the sulfur−carbon(vinyl) bond of BT and the recent observations of insertion into the sulfur−carbon(aryl) bond. The results indicate that insertion selectivity is governed by several factors, including the orbital structure of BT, steric interactions between the metal and the heterocycle, and the metal−carbon bond strengths of the inserted products. In most cases, all three factors support the experimentally observed preference for insertion into the S−C(vinyl) bond. Subtle structural changes, however, can lead to S−C(aryl) metal-inserted products. For instance, steric factors inhibiting insertion of metal fragments into the sulfur−carbon(aryl) bond of BT can be overcome by “tied back” or relatively small metal fragments. In addition, the strength of the metal−carbon bond of the inserted product, which appears to be a determining factor leading to the otherwise unexpected sulfur−carbon(aryl) metal-inserted adducts, can be influenced by derivatizing BT or coordinating metals to the arene ring of BT.

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Analysis of a hydrodesulfurization process— 2 [1]. The reactions of 2- and 3-methylthiophenes with tris(triethylphosphine)platinum(0)

Cited by 35 publications

References 23 publications

Ring Opening of Methylbenzothiophenes and Methyldibenzothiophenes by Tris(triethylphosphine)platinum(0)

Ring Opening of Methylbenzothiophenes and Methyldibenzothiophenes by Tris(triethylphosphine)platinum(0)

New hydrogenation and isomerization reactions involving thiaplatinacycles derived from benzothiophene

Ab Initio Molecular Orbital Study of Organometallic Complexes Containing Benzo[b]thiophene

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