Chemistry of Compounds with Silicon–Sulphur, Silicon–Selenium and Silicon–Tellurium Bonds

Armitage, David

doi:10.1002/0470857250.ch31

The Chemistry of Organic Silicon Compounds

1998

DOI: 10.1002/0470857250.ch31

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Chemistry of Compounds with Silicon–Sulphur, Silicon–Selenium and Silicon–Tellurium Bonds

David Armitage¹

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Cited by 7 publications

(3 citation statements)

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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).…”

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

2014

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“…A widely used method is salt elimination from chlorosilane and metal thiolate such as lithium thiolate. 4 This method produces a salt such as LiCl as a byproduct, and thiol should be converted into metal thiolate prior to the salt elimination reaction. In contrast, dehydrogenative coupling of thiol and hydrosilane catalyzed by a transition metal complex seems to be more convenient.…”

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Dehydrogenative Coupling of Thiol with Hydrosilane Catalyzed by an Iron Complex

et al. 2011

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“…Thiosilanes are usually obtained through a stoichiometric reaction of chlorosilane and a metal thiolate, such as lithium thiolate. 13 This procedure requires the prior formation of the metal thiolate, which is a significant shortcoming. In order to develop a more convenient methodology, a catalytic approach has been reported.…”

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Efficient ruthenium-catalysed S–S, S–Si and S–B bond forming reactions

2013

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[RuCl(PPh3)2(3-phenylindenyl)] (1) has been shown to be an efficient catalyst in thiol dehydrogenative coupling to give disulfides. Moreover, an efficient procedure for the preparation of silylthioethers and thioboranes is presented. Complex 1 demonstrated a great ability to catalyse the coupling of thiols with silanes and boranes under mild conditions with excellent results (turnover number up to 200).

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Chemistry of Compounds with Silicon–Sulphur, Silicon–Selenium and Silicon–Tellurium Bonds

Cited by 7 publications

References 65 publications

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

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

Dehydrogenative Coupling of Thiol with Hydrosilane Catalyzed by an Iron Complex

Efficient ruthenium-catalysed S–S, S–Si and S–B bond forming reactions

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Chemistry of Compounds with Silicon–Sulphur, Silicon–Selenium and Silicon–Tellurium Bonds

Cited by 7 publications

References 65 publications

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

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

Dehydrogenative Coupling of Thiol with Hydrosilane Catalyzed by an Iron Complex

Efficient ruthenium-catalysed S–S, S–Si and S–B bond forming reactions

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Product

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

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