Cluster versus non-cluster catalysis in olefin thermal isomerization and hydrosilylation in the presence of Ru3(CO)12

Hilal, Hikmat S.; Khalaf, Shukri; Jondi, Waheed

doi:10.1016/0022-328x(93)83186-y

Cited by 38 publications

(18 citation statements)

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“…Other transition metal complexes also can be used as catalysts, such as the hydrosilylation reaction with complexes of rhodium [ 6 , 7 ], ruthenium [ 8 , 9 , 10 ], palladium [ 11 , 12 ], nickel [ 13 ], iron [ 14 ], iridium [ 15 , 16 ], examples are presented in Figure 4 . There are cases of the reaction proceeding according to the modified Chalk and Harrod mechanism [ 17 ], in which the reaction rate is determined by the introduction of alkenes through M–Si bonds.…”

Section: Overview Of Hydrosilylationmentioning

confidence: 99%

“…It represents a complex of platinum with an alkenyl functional group, which undergoes the following transformations in the catalytic cycle: I HS -oxidative addition of Si-H bonds to platinum; II HS -migratory insertion of the coordinated alkene to Pt-H bond; III HS -reductive elimination with the formation of Si-C bonds; The mechanism of this transformation is presented in Figure 3. Other transition metal complexes also can be used as catalysts, such as the hydrosilylation reaction with complexes of rhodium [6,7], ruthenium [8][9][10], palladium [11,12], nickel [13], iron [14], iridium [15,16], examples are presented in Figure 4. There are cases of the reaction proceeding according to the modified Chalk and Harrod mechanism [17], in which the reaction rate is determined by the introduction of alkenes through M-Si bonds.…”

Section: The General Mechanism Of Action Of Organometallic Catalysts In Hydrosilylation Processesmentioning

confidence: 99%

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Platinum-Catalyzed Hydrosilylation in Polymer Chemistry

et al. 2020

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This paper addresses a review of platinum-based hydrosilylation catalysts. The main field of application of these catalysts is the curing of silicone polymers. Since the 1960s, this area has developed rapidly in connection with the emergence of new polymer compositions and new areas of application. Here we describe general mechanisms of the catalyst activity and the structural effects of the ligands on activity and stability of the catalysts together with the methods for their synthesis.

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Section: Overview Of Hydrosilylationmentioning

confidence: 99%

Section: The General Mechanism Of Action Of Organometallic Catalysts In Hydrosilylation Processesmentioning

confidence: 99%

Platinum-Catalyzed Hydrosilylation in Polymer Chemistry

et al. 2020

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“…Olefin hydrosilylation reactions are known to occur with the aid of a homogeneous and supported catalyst (20,21). These reactions are conventionally known to be accomplished by other side reactions, such as olefin isomerization.…”

Section: Introductionmentioning

confidence: 99%

The activity of Pt/SiO₂ catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

González-Jiménez¹,

Martínez-Rosales²,

Cervantes³

2003

Can. J. Chem.

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Heterogeneous platinum catalysts (Pt/SiO 2 ) obtained by the sol-gel process at pH 3 and 9 have been used in the hydrosilylation reaction of 1-alkynes using various silanes. Once the catalysts were activated they were used in the hydrosilylation of 1-alkynes after a short induction period. The product distribution was quite similar in either case but important differences in catalytic activity and turnover reactions were observed. The catalyst obtained in the basic medium after each reaction lost its catalytic activity, so further activation was needed. To understand this behavior, the catalysts were characterized by 29 Si CPMAS NMR, FT IR, and BET surface area measurements. The 29 Si CPMAS NMR studies showed the presence of terminal and bridged hydroxyl groups in the Pt/SiO 2 catalyst at pH = 9. Similar results were observed by FT IR analysis because of the catalysts' synthetic conditions. Résumé : On a utilisé des catalyseurs homogènes de platine (Pt/SiO 2 ) obtenus par le procédé sol-gel à des pH de 3 et de 9 pour effectuer l'hydrosilylation d'alc-1-ynes à l'aide de divers silanes. Une fois les catalyseurs activés, ils étaient utilisés pour effectuer l'hydrosilylation des alc-1-ynes après une courte période d'induction. La distribution des produits est très semblable dans les deux cas, mais on a observé des différences importantes dans l'activité catalytique et dans les réactions de changement. Le catalyseur obtenu en milieu basique perd son activité après chaque réaction et on doit donc procéder à chaque fois à une nouvelle activation. Dans le but de comprendre ce comportement, on a procédé à une caractérisation des catalyseurs par RMN « CPMAS » du 29 Si, par spectroscopie IR à transformée de Fourrier et par des mesures « BET » de l'aire de la surface. Les études de RMN CPMAS du 29 Si ont montré que la présence de groupes hydroxyles pontés et terminaux est minimale dans le catalyseur de Pt/SiO 2 obtenu à un pH de 9. Des résultats semblables ont été obtenus par l'analyse du spectre IR à transformée de Fourier en raison des conditions de synthèse du catalyseur.

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“…Several studies have described the use of metal carbonyl cluster complexes as catalyst precursors for hydrosilylation reactions, − but the hydrosilylation of alkynes by mixed-metal cluster complexes has been studied in only a few cases. Ojima and co-workers reported the hydrosilylation of 1-hexyne by rhodium−cobalt mixed-metal clusters, resulting in a mixture of α- and β-isomers (eq 1) …”

Section: Introductionmentioning

confidence: 99%

Catalytic Hydrosilylation of Diarylalkynes by Layer-Segregated Platinum−Ruthenium Cluster Complexes Pt₃Ru₆(CO)₂₀(μ₃-RC₂R)(μ₃-H)(μ-H)

Adams

Barnard

1998

Organometallics

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It has been found that the layer-segregated platinum-ruthenium cluster complex Pt 3 -Ru 6 (CO) 20 (µ 3 -PhC 2 Ph)(µ 3 -H)(µ-H), 2a, is an effective catalyst for the hydrosilylation of diphenylacetylene by triethylsilane to yield (E)-[(1,2-diphenyl)ethenyl]triethylsilane at a turnover frequency, TOF (TON/h), of 29 h -1 . The activation parameters, ∆H q ) 17(2) kcal/ mol and ∆S q ) -18(5) eu, were established. Small amounts of cis-stilbene were also formed. A kinetic analysis showed the reaction is first order in cluster and silane concentrations but zero order in alkyne concentration. The reaction is strongly inhibited by CO but is unaffected by mercury. A mechanism involving CO dissociation, silane oxidative addition, alkyne addition, a Si-C bond-forming step, and silylolefin dissociation is proposed with all transformations occurring at a ruthenium triangle. Pt 3 Ru 6 (CO) 20 (µ 3 -TolC 2 Tol)(µ 3 -H)(µ-H), 2b, was also found to be an effective catalyst for the hydrosilylation of TolC 2 Tol to (E)-Tol-(H)C 2 (SiEt 3 )Tol, TOF of 32 h -1 . Ru 3 (CO) 9 (µ 3 -PhC 2 Ph)(µ-H) 2 and PtRu 2 (CO) 8 (µ 3 -PhC 2 Ph)-(dppe) are relatively poor catalysts, TOF ) 3.9 and 2.3 h -1 , respectively. [NBu 4 ][Pt 3 -Ru 6 (CO) 20 (µ 3 -PhC 2 Ph)(µ-H)], 3, formed by deprotonation of 2a, also exhibits good catalytic activity, but its catalysis is inhibited by mercury, which may be indicative of heterogeneous catalysis.

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Cluster versus non-cluster catalysis in olefin thermal isomerization and hydrosilylation in the presence of Ru3(CO)12

Cited by 38 publications

References 22 publications

Platinum-Catalyzed Hydrosilylation in Polymer Chemistry

Platinum-Catalyzed Hydrosilylation in Polymer Chemistry

The activity of Pt/SiO₂ catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

Catalytic Hydrosilylation of Diarylalkynes by Layer-Segregated Platinum−Ruthenium Cluster Complexes Pt₃Ru₆(CO)₂₀(μ₃-RC₂R)(μ₃-H)(μ-H)

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Cluster versus non-cluster catalysis in olefin thermal isomerization and hydrosilylation in the presence of Ru3(CO)12

Cited by 38 publications

References 22 publications

Platinum-Catalyzed Hydrosilylation in Polymer Chemistry

Platinum-Catalyzed Hydrosilylation in Polymer Chemistry

The activity of Pt/SiO2 catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

Catalytic Hydrosilylation of Diarylalkynes by Layer-Segregated Platinum−Ruthenium Cluster Complexes Pt3Ru6(CO)20(μ3-RC2R)(μ3-H)(μ-H)

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The activity of Pt/SiO₂ catalysts obtained by the sol-gel method in the hydrosilylation of 1-alkynes

Catalytic Hydrosilylation of Diarylalkynes by Layer-Segregated Platinum−Ruthenium Cluster Complexes Pt₃Ru₆(CO)₂₀(μ₃-RC₂R)(μ₃-H)(μ-H)