Carbonsulfur bond cleavage in CpRu(η5-thiophene)+ and subsequent reactions of the butadiene-thiolate product

Hachgenei, Johannes; Angelici, Robert J.

doi:10.1016/0022-328x(88)89037-5

Cited by 53 publications

(33 citation statements)

References 33 publications

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“…The P 3 Ru grouping of the ( fac -triphos)Ru fragment has an approximate C 3 v symmetry with three P−Ru−P angles in the range 86.23(8)−90.60(7)°. The Ru−S bond distance (2.428(2) Å) is comparable to those of ruthenium−thiolate complexes, in particular, it is quite similar to the Ru−S distance in the C−S-inserted 2,5-dimethylthiophene complex [CpRu(PPh 2 Me) 2 {η 1 -SC(Me)CHCH(Me)}] (2.44(6) Å) 6b. No bonding interaction is envisaged between the Ru and B atoms (2.473(9) Å) .…”

Section: Resultsmentioning

confidence: 59%

“…Despite many recent research efforts in this direction, information on the reactivity of ruthenium complexes toward thiophenic substrates is still scarce and essentially limited to the reactions with thiophene (T). Both C−H and C−S , bond cleavage reactions of T have been reported to take place at ruthenium. However, in no case has the rupture of T been observed to occur by direct C−S insertion of ruthenium.…”

Section: Introductionmentioning

confidence: 99%

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C−S Bond Cleavage of Benzo[b]thiophene at Ruthenium

et al. 1998

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The ruthenium(II) (tetrahydroborate)hydride complex [(triphos)RuH(BH4)] (1) reacts with benzo[b]thiophene (BT) in THF at 40 °C yielding, after 3 h, a mixture of four different compounds: [(triphos)RuH{BH3(o-S(C6H4)CH2CH3)}] (2), [(triphos)Ru{η4-S(C6H4)CH(CH3)}] (3), [(triphos)RuH(μ-S(C6H4)CH2CH3)2HRu(triphos)] (4), and [(triphos)RuH(μ-BH4)HRu(triphos)]+ (5 + ) (triphos = MeC(CH2PPh2)3). After two further hours of reaction, 3 disappears and is completely converted to 4. Further heating at 40 °C does not change the product composition (2, 4, and 5 + in a 4:1.3:3 ratio). A variety of independent reactions with isolated compounds have been performed with the aim of elucidating the mechanism of the C−S insertion/hydrogenation of BT to the 2-ethylthiophenolate ligand. The μ-thiolate complex 4 reacts in THF with dihydrogen (≥160 °C, 30 bar H2) or with HBF4·OEt2 (20 °C) yielding ethylbenzene and 2-ethylthiophenol, respectively. No reaction occurs with LiHBEt3. All of the reactions and new complexes reported have been studied by multinuclear NMR spectroscopy. An X-ray analysis has been carried out on a single crystal of 2.

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Section: Resultsmentioning

confidence: 59%

Section: Introductionmentioning

confidence: 99%

C−S Bond Cleavage of Benzo[b]thiophene at Ruthenium

et al. 1998

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“…salt metathesis with LiCp* however,t here is no report on the use of LiCp* in the literature for this example. Instead, TlCp* [32,33] and (nBu) 3 SnCp* [34] were used as Cp* source,m ost likely to avoid the nucleophilic attack at the coordinated benzene. [33,[35][36][37] Inspired by the literature known reactionw ith (nBu) 3 SnCp*, [34] we changedt he solventt o tetrahydrofuran and added 2equivalents of LiCp* relative to [(C 6 H 6 )RuCl 2 ] 2 and stirred the mixture at room temperature for 2h (see Scheme 8).…”

Section: Recycling Of the Air Stable Ligandmentioning

confidence: 99%

Electron‐Deficient Imidazolium Substituted Cp Ligands and their Ru Complexes

Mazzotta

Zitzer

Speiser

et al. 2020

Chemistry A European J

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The synthesis of electron-poorm ono-, di-and tri-(imidazolium)-substituted Cp-ylides is presented and their electronic properties are discussed based on NMRs pectroscopy,X-ray structurea nalyses, electrochemical investigations and DFT calculations as well as by their reactivity toward [Ru(CH 3 CN) 3 Cp*](PF 6). With mono-and di(imidazolium)-substituted cyclopentadienides the respective monocationic and dicationic ruthenocences are formed (X-ray), whereas tri(imi-dazolium)c yclopentadienides are too electron-poor to form the ruthenocenes.C yclic voltammetric analysiso ft he ruthenocenes shows reversible oxidation at ap otentialt hat increasesw ith every additional electron-withdrawing imidazolium substituent at the Cp ligand by 0.53-0.55 Vi na ne lectrolyte based on aw eakly coordinating anion. Ar eversible oxidation can be observed for the free 1,3-disubstituted ligand as well.

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“…Other metals, such as Ru, Os, Rh, and Ir, are known to produce better catalysts, but are not used due to their increased expense . While many homogeneous systems have been explored to model the HDS process, few of these have focused on the use of ruthenium as the active species. − …”

Section: Introductionmentioning

confidence: 99%