Nickel(II) complexes as catalysts in the hydrosilylation of olefins

Kumada, Makoto; Kiso, Yoshihisa; Umeno, Masayuki

doi:10.1039/c29700000611

Cited by 28 publications

(7 citation statements)

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“…All reagents and solvents were used as purchased from commercial suppliers. The compounds 1,1‘-bis(dimethylphosphino)ferrocene (dmpf), bis(diethylphosphino)ferrocene (depf), bis(diisopropylphosphino)ferrocene (dippf), PdCl(Me)(COD) (COD = cycloocta-1,5-diene), PdCl 2 (dippf) 10 ( 3 ), PdCl(Me)(depf) 18b ( 9 ), and PdCl(Me)(dippf) 15 ( 10 ) were synthesized according to published procedures. Carbonylation reactions were performed with a 325 mL stainless steel autoclave, constructed at the ICCOM-CNR (Firenze, Italy), equipped with a magnetic drive stirrer and a Parr 4842 temperature and pressure controller.…”

Section: Methodsmentioning

confidence: 99%

Ethylene Carbonylation in Methanol and in Aqueous Media by Palladium(II) Catalysts Modified with 1,1‘-Bis(dialkylphosphino)ferrocenes

Bianchini¹,

Meli²,

Oberhauser³

et al. 2005

Organometallics

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Palladium(II) complexes with the formula [Pd(H 2 O)(OTs)(P-P)]OTs, where P-P is 1,1′-bis-(dimethylphosphino)ferrocene (dmpf), 1,1′-bis(diethylphosphino)ferrocene (depf), or 1,1′-bis-(diisopropylphosphino)ferrocene (dippf), have been synthesized and used to catalyze the carbonylation of ethylene in MeOH, water, or a 1/1 water/1,4-dioxane mixture. In MeOH, the reactions catalyzed by the dmpf and depf complexes gave alternating polyketone (alt-E-CO), while methyl propanoate and 3-pentanone were selectively produced with the dippf catalyst. The last catalyst was inactive in aqueous solvent. In contrast, the dmpf and depf catalysts were active in either water or water/1,4-dioxane for the copolymerization of CO with ethylene. These two catalysts were efficient also for the terpolymerization of CO with ethylene and propene in MeOH or water/1,4-dioxane. Operando high-pressure NMR experiments and in situ reactions with model compounds have provided useful information to rationalize the activity and selectivity of the catalytic systems investigated.

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Section: Methodsmentioning

confidence: 99%

Ethylene Carbonylation in Methanol and in Aqueous Media by Palladium(II) Catalysts Modified with 1,1‘-Bis(dialkylphosphino)ferrocenes

Bianchini¹,

Meli²,

Oberhauser³

et al. 2005

Organometallics

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“… Such a hydrosilylation product, although it can be Si-alkylated by a standard nucleophilic substitution, has found little use. In parallel, Kumada was working with the same reagents and reported that, using [NiCl 2 (dmpf)] (dmpf being a rigid 1,1′-bis(dimethylphosphino)ferrocene ligand), the only product of hydrosilylation is formed in an anti-Markovnikov (β) manner . Nickel complexes bearing simple phosphines were also used by Hetflejš but gave α products only in minor amounts …”

Section: General Approachesmentioning

confidence: 99%

Markovnikov Hydrosilylation of Alkenes: How an Oddity Becomes the Goal

2018

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Over the years, hydrosilylation of terminal alkenes has emerged as one of the most prominent applications of homogeneous catalysis. While most of the relevant reports concern β-selective hydrosilylation, yielding linear products which are of industrial importance, the opposite selectivity is also gaining increasing interest and sets the scene for the next challenges. Markovnikov hydrosilylation of alkenes, especially in its asymmetric variant, has become the aim of development of new catalytic systems successfully implementing base-metal complexesone of the most prominent trends in contemporary catalysis. In this Perspective, we present the current state of this topic and the way it has been achieved, with special emphasis put on the issues still unresolved and prospective directions of development based on the trends present in the literature, but without unnecessary attention to some details of only historical significance.

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“…The direction of addition to styrene also depends on the CH 3 2RCH=CH 2 4-2HSiCl 2 CH 3 ► RCH 2 CH 2 SiCl 2 CH 3 + RCHSiCl 2 CH 3 nature of the ligand present (299). In the first case a mixture of 3-and 4-silylcyclohexene is obtained and in the second, the three possible substituted cyclooctenes (302)(303)(304)310). CH 3 ^ CH 3 C e H 5 C=CH 2 + HSiCl 2 CH 3 tC 6 H 6 CH^(CH 3 )CeH 5 ] a NiCi 2 } C e H e J : _ C H a S i c l a C H 8 H Hydrosilylation is accompanied by olefin isomerization and exchange of a silicon-bonded chlorine atom for a hydrogen atom.…”

Section: Mil the Hydrosilylation And Hydrocyanation Of Olefinsmentioning

confidence: 99%