Ruthenium carbonyl-catalysed Si–heteroatom X coupling (X = S, O, N)

Toh, Chun Keong; Poh, Hwa Tiong; Lim, Ching Si; Fan, Wai Yip

doi:10.1016/j.jorganchem.2012.07.024

Cited by 27 publications

(16 citation statements)

References 35 publications

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“…To date, several catalysts for the cross‐coupling reaction of hydrosilanes with amines have been developed and some improvements have been made in catalytic performance 2. However, these catalysts still have suffered from problems in low activities,2b–d,h–j,m limitations of substrate applicability2a–l and necessity of excess amounts of hydrosilanes or amines for the high‐yielding coupling. With regard to the coupling reaction of hydrosilanes with amides, only one catalytic method has been reported despite the utility of silylamides 3.…”

Section: Dehydrogenative Coupling Of 1 With 2 Using Various Catalystsmentioning

confidence: 99%

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

Mitsudome

Urayama

Maeno

et al. 2015

Chemistry A European J

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Hydroxyapatite-supported gold nanoparticles (Au/HAP) can act as a highly active and reusable catalyst for the coupling of hydrosilanes with amines under mild conditions. Various silylamines can be selectively obtained from diverse combinations of equimolar amounts of hydrosilanes with amines including less reactive bulky hydrosilanes. This study also highlights the applicability of Au/HAP to the selective synthesis of silylamides through the coupling of hydrosilanes with amides, demonstrating the first example of an efficient heterogeneous catalyst. Moreover, Au/HAP shows high reusability and applicability for gram-scale synthesis.

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Section: Dehydrogenative Coupling Of 1 With 2 Using Various Catalystsmentioning

confidence: 99%

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

Mitsudome

Urayama

Maeno

et al. 2015

Chemistry A European J

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“…Only a few catalytic systems have been developed for this purpose. 65 , 66 Several thiols and silanes are well tolerated by the dehydrogenative coupling system, achieving high conversion in all cases. In fact, this transformation gave the best TON reported to date (TON = 200) (Scheme 21 ).…”

mentioning

confidence: 99%

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

2014

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ConspectusOne of the most important challenges in catalyst design is the synthesis of stable promoters without compromising their activity. For this reason, it is important to understand the factors leading to decomposition of such catalysts, especially if side-products negatively affect the activity and selectivity of the starting complex. In this context, the understanding of termination and decomposition processes in olefin metathesis is receiving significant attention from the scientific community. For example, the decomposition of ruthenium olefin metathesis precatalysts in alcohol solutions can occur during either the catalyst synthesis or the metathesis process, and such decomposition has been found to be common for Grubbs-type precatalysts. These decomposition products are usually hydridocarbonyl complexes, which are well-known to be active in several transformations such as hydrogenation, terminal alkene isomerization, and C–H activation chemistry. The reactivity of these side products can be unwanted, and it is therefore important to understand how to avoid them and maybe also important to keep an open mind and think of ways to use these in other catalytic reactions.A showcase of these decomposition studies is reported in this Account. These reports analyze the stability of ruthenium phenylindenylidene complexes, highly active olefin metathesis precatalysts, in basic alcohol solutions. Several different decomposition processes can occur under these conditions depending on the starting complex and the alcohol used. These indenylidene-bearing metathesis complexes display a completely different behavior compared with that of other metathesis precatalysts and show an alternative competitive alcoholysis pathway, where rather than forming the expected hydrido carbonyl complexes, the indenylidene fragment is transformed into a η1-indenyl, which then rearranges to its η5-indenyl form. In particular, [RuCl(η5-(3-phenylindenylidene)(PPh3)2] has been found to be extremely active in numerous transformations (at least 20) as well as compatible with a broad range of reaction conditions, rendering it a versatile catalytic tool. It should be stated that the η5-phenyl indenyl ligand shows enhanced catalytic activity over related half-sandwich ruthenium complexes. The analogous half-sandwich (cyclopentadienyl and indenyl) ruthenium complexes show lower activity in transfer hydrogenation and allylic alcohol isomerization reactions. In addition, this catalyst allows access to new phenylindenyl ruthenium complexes, which can be achieved in a very straightforward manner and have been successfully used in catalysis. This Account provides an overview of how mechanistic insights into decomposition and stability of a well-known family of ruthenium metathesis precatalysts has resulted in a series of novel and versatile ruthenium complexes with unexpected reactivity.

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“…In 2012, Toh et al. reported that a commercially available triruthenium carbonyl cluster [Ru(CO) 12 ] could be used as an effective catalyst for N‐, O‐, and S‐silylation . A year later, Nolan and co‐workers synthesized a highly stable [RuCl(PPh 3 )2‐(3‐phenylindenyl)] complex that also turned out to be an effective catalyst for the formation of silylthioethers by Si−S dehydrocoupling .…”

Section: Silicon–sulfur Bond Formationmentioning

confidence: 99%

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

Kuciński

Hreczycho

2017

ChemCatChem

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Silicon and its compounds with other heteroatoms have received considerable attention, particularly because of their applicative ability. Silicon forms a large number of compounds with other p‐block elements (e.g., C, N, S, O, F, Cl, and others). All of them affect practical chemistry to some extent and are characterized by unique properties. This article highlights recent developments and covers the literature from the last 10 years. It is mainly focused on catalytic methods for silicon–nitrogen, silicon–phosphorus, silicon–oxygen, and silicon–sulfur bond formation. The scope and applications of these practical compounds will also be discussed.

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Ruthenium carbonyl-catalysed Si–heteroatom X coupling (X = S, O, N)

Cited by 27 publications

References 35 publications

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

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Ruthenium carbonyl-catalysed Si–heteroatom X coupling (X = S, O, N)

Cited by 27 publications

References 35 publications

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

Highly Efficient Dehydrogenative Coupling of Hydrosilanes with Amines or Amides Using Supported Gold Nanoparticles

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

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From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η⁵-indenyl)(PPh₃)₂Cl] Story