Ru-Catalyzed Dehydrogenative Silylation of POSS-Silanols with

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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Ru-Catalyzed Dehydrogenative Silylation of POSS-Silanols with Hydrosilanes: Its Introduction to One-Pot Synthesis Joanna Kaźmierczak, Krzysztof Kucinś ki,* Dariusz Lewandowski, and Grzegorz Hreczycho* Faculty of Chemistry, Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614 Poznań, Poland

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ABSTRACT: A commercially available and stable ruthenium dodecacarbonyl catalyst (Ru3(CO)12) allows very efficient and convenient access to functionalized silsesquioxanes (SQs) containing siloxane moiety (Si−O−Si) via dehydrogenative coupling of POSS-silanols with hydrosilanes. With the aid of SiH-containing silsesquioxanes, an unprecedented one-pot procedure has been revealed, and the usefulness of this approach was demonstrated by the synthesis of various derivatives via O-silylation, as well as CC and CN hydrosilylation.

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INTRODUCTION POSS (polyhedral oligomeric silsesquioxanes) represent one of the most investigated groups among silicon compounds. They have attracted a lot of attention due to their unique features and the possibility of applying them as precursors to nanocomposites.1−5 Therefore, the novel methods of POSS synthesis and functionalization, as well as their use in material chemistry, are a key part of current scientific studies in this field.6−16 Of the different methods, the conventional approaches for the synthesis of SQs and their further functionalization are mainly based on the hydrolytic condensation of halosilanes or alkoxysilanes.1,6 The most fundamental disadvantage of these solutions is the formation of highly reactive and volatile byproducts as hydrogen halides. Because of this, it is necessary to use large amounts of bases. What is more, most of these methods suffer from poor selectivity and low functional group tolerance. Therefore, novel approaches for the synthesis and functionalization of POSS molecules are being developed, taking into account the utilization of less sensitive reagents. Our research team has recently placed a strong focus on the use of metal triflates (especially Sc(OTf)3) and Nafion as catalysts in O-silylation, Ogermylation, and O-borylation of silanols and POSS-silanols.17−24 The mentioned protocols allow us to obtain a library of unsymmetrical disiloxanes, symmetrical tri- and tetrasiloxanes, oligosiloxanes, germasiloxanes, borasiloxanes, and functionalized SQs under extremely mild conditions (rt). In most of these routes, several 2-methylallylsilanes were utilized. These derivatives are known as very effective silylating agents,25,26 as well as their vinyl analogues.27−31 However, it seems clear that the possibility of applying the hydrosilanes would allow one to develop even more atom-economic processes. The methods describing the silylation of alcohols and phenols are well known.32−37 On the other hand, in the case of silanols this has not been extensively investigated. Michalska reported that homogeneous and silica-supported rhodium(I) complexes © XXXX American Chemical Society

might be used for the reaction of several silanols with a series of various hydrosilanes.38 Anderson et al. described a direct conversion of hydride-terminated silicon quantum dots mediated by radical initiators.39 Recently, the Shimada group has reported a pioneering work on the selective synthesis of hydro-substituted siloxanes and SQs by Au-catalyzed dehydrogenative cross-coupling reaction of hydrosilanes with compounds containing silanol groups.40 Also worthy of note is the comprehensive use of B(C6F5)3 as the catalyst in the processes utilizing silanols41,42 and alkoxysilanes.43,44 That idea was subsequently developed by the Shimada group to synthesize a library of sequence-controlled oligosiloxanes via a one-pot procedure.45−47 Finally, Shankar et al. reported the conversion of hydrosilanes into poly(siloxanes) mediated by gold and palladium nanoparticles.48,49 In this context, the additional benefits related to one-pot procedures also need to be underlined.50−56 Higher efficiency, easier purification process, as well as higher yields are among them. In this paper, we present a highly chemoselective and efficient method for the dehydrogenative coupling of a variety of hydrosilanes with POSS silanols catalyzed by the commercially available and stable ruthenium dodecacarbonyl catalyst (Ru3(CO)12). This allows very efficient and convenient access to functionalized silsesquioxanes containing siloxane moiety. Furthermore, the SiH-containing SQs have been simultaneously transformed via unprecedented one-pot procedures based on O-silylation, as well as CC and CN hydrosilylation reactions (Figure 1).

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MATERIALS AND METHODS

The catalyst and reagents used for the experiments were purchased from Sigma-Aldrich Co. POSS compounds were obtained from Hybrid Plastics. Reactions were carried out under argon atmosphere. The Received: September 17, 2018

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DOI: 10.1021/acs.inorgchem.8b02645 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

Figure 1. One-pot pathway to functionalized silsesquioxanes mediated by Ru3(CO)12. structure of products was determined by NMR spectroscopy. The 1H NMR (400 MHz), 13C NMR (101 MHz), and 29Si NMR (79 MHz) spectra were recorded on a Bruker Avance III HD NanoBay spectrometer, using C6D6 as the solvent. General Procedure for the Synthesis of Compounds 1−14. To a 25 mL Schlenk flask equipped with a stirring bar, POSS monosilanol (1.0 mmol, 1.0 equiv), hydrosilane (1.5 mmol, 1.5 equiv, products 1−10 and 13−14) or dihydrosilane (2.0 mmol, 2 equiv, products 11 and 12), and 2 mL of toluene were added under argon atmosphere. Subsequently, Ru3(CO)12 (0.04 mmol, 4 mol %) was added, and the reaction mixture was stirred at 120 °C for 24 h. After this time, the solvent and all volatiles were evaporated under reduced pressure. Next, the product was separated from the catalyst and the excess of silane by adding acetonitrile (2 mL). The desired product is not soluble in acetonitrile in contrast to other substances in the reaction mixture (i.e., catalyst, remained substrates, and traces of symmetrical disiloxanes). Finally, the crude products were separated from the filtrate and dried under reduced pressure to give the corresponding compounds 1−14. The general procedure for products 15−17 was exactly the same (in this case 3 equiv of hydrosilane was used). The functionalized SQs (1−4, 6−11, and 15−17) are known in the literature.20,23,57−59 The functionalized SQs 5 and 12−14 are new derivatives. General Procedure for the One-Pot Synthesis of Compounds 18−24. To a 25 mL Schlenk flask equipped with a stirring bar, POSS monosilanol (1.0 mmol, 1.0 equiv), diethylsilane (1.5 mmol, 1.5 equiv), and 2 mL of toluene were added under argon atmosphere. Subsequently, Ru3(CO)12 (0.04 mmol, 4 mol %) was added, and the reaction mixture was stirred at 120 °C for 24 h. After this time, excess (4−5 equiv) reagent (i.e., vinylsilane, olefin, benzothiazole, silanol, or alcohol) was added, and the reaction mixture was stirred at 120 °C for 24 h. Then, the solvent and all volatiles were evaporated under reduced pressure. Next, the product was separated from the catalyst and the excess of substrate by adding acetonitrile (2 mL). The desired product is not soluble in acetonitrile in contrast to other substances in the reaction mixture (i.e., catalyst, remained substrates, traces of symmetrical disiloxanes, and hydrosilylation/silylation byproducts). Finally, the crude products were separated from the filtrate and dried under reduced pressure to give the corresponding compounds 18−24 (new derivatives).

Table 1. Comparison of the Catalytic Activity of Ruthenium Complexes in Dehydrogenative Coupling of POSS Monosilanol with Dimethylphenylsilanea

RuCl2(p-cymene)]2

Ru3(CO)12

catalyst loading (mol %)

T (°C)

conversion (%)b

catalyst loading (mol %)

T (°C)

conversion (%)b

2 2 4 4

80 120 80 120

traces traces traces traces

2 2 4 4

80 120 80 120

traces 50 traces 98

a

24 h in toluene. bDetermined by crude NMR.

of POSS mono- and disilanols with several hydrosilanes. The results are summarized in Table 2. All of the POSS silanols underwent the dehydrogenative coupling with several hydrosilanes in the presence of 4 mol % Ru3(CO)12 (monosilanols) or 8 mol % Ru3(CO)12 (disilanols) and afforded the corresponding siloxyl-substituted SQs in excellent yields (81−98%) with high chemoselectivity (Table 3, all entries). Notably, the reactions of dihydrosilanes (Table 2, products 11 and 12) led exclusively to SQs bearing SiH functionalities. The remaining excess of hydrosilane was easily removed under reduced pressure. Having developed a good siloxane-bond-forming reaction, we next focused on a one-pot synthesis. The use of Ru3(CO)12 in organosilicon chemistry is well described in the literature.61−66 Because of that, we decided to investigate a one-pot idea utilizing a two-step pathway, namely, the dehydrogenative coupling of POSS silanol with dihydrosilane (the formation of SQs bearing SiH group) and subsequent use of obtained derivatives in Osilylation or hydrosilylation reactions (Figure 2). The hypothesis mentioned above was successfully verified as summarized in Table 3. In the presence of 4 mol % Ru3(CO)12, the dehydrogenative cross-coupling of POSS monosilanol with diethylsilane afforded SQs bearing SiH functionalities. After completion of this step, the remaining Si−H group was subsequently utilized in a CC hydrosilylation (products 18−20), a CN hydrosilylation (product 21), and a consecutive dehydrogenative coupling with alcohols (product 24) and silanols (products 22 and 23). All reactions were carried out successively in a single flask without any additional workup. What is more, an amount of ruthenium cluster (4 mol %) added during the first step was also sufficient to promote the second step of these transformations. In this procedure the remaining substrate bearing SiH functionality also undergoes the hydrosilylation or silylation reaction; however, formed byproduct as well as remaining olefins are highly soluble in acetonitrile and

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RESULTS AND DISCUSSION As a starting point, we chose to start with the optimization of the process. Encouraged by the work reported by Ojima et al. (about the dehydrogenative silylation of alcohols and carboxylic acids),60 we decided to examine commercially available and stable ruthenium catalysts, namely, (p-cymene)ruthenium dichloride dimer ([RuCl2(p-cymene)]2) and ruthenium dodecacarbonyl cluster (Ru3(CO)12). We considered the reaction between dimethylphenylsilane (1.5 equiv) with POSS monosilanol (1.0 equiv) under various conditions. The results are summarized in Table 1. We found that the reaction gives the best results only for the ruthenium cluster (Table 1). This transformation was carried out in toluene due to the high temperature of the reaction (120 °C) and excellent solubility of the SQs. With the optimized conditions achieved, we then proceeded to examine the generality of the ruthenium-mediated dehydrogenative coupling B


Article

Inorganic Chemistry Table 2. Ru-Catalyzed O-Silylation of POSS Silanols with Hydrosilanesa

Conditions: toluene, Ru3(CO)12 4 mol % (monosilanols) or 8 mol % (disilanols), argon atmosphere, 120 °C, and 24 h. Molar ratio of the POSS monosilanol/silane reagent ratio is 1.0:1.5. Molar ratio of the POSS disilanol/silane reagent ratio is 1.0:3.0. bIsolated yields of compounds 1−17.

a

dihydrogen molecule is released (the formation of dihydrogen was confirmed by a 1H NMR singlet at 4.47 ppm).

can be easily separated from the desired product (which is insoluble). On the basis of our previous results62 and published literature,38,64,67,68 the following mechanism is proposed (Figure 3). We have already confirmed the oxidative addition of the hydrosilane to ruthenium cluster that affords the ruthenium hydride complex, and this actually has also been recognized by other groups.64,68,69 This is probably followed by a nucleophilic attack of the POSS silanol group on the silicon atom in the silyl ligand. Finally, a new siloxane moiety is formed, and a simple

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CONCLUSIONS In summary, a novel approach to introduce siloxyl functionalities into silsesquioxanes has been developed. A commercially available and stable ruthenium dodecacarbonyl catalyst [Ru3(CO)12] allows very efficient and convenient access to functionalized silsesquioxanes via a dehydrogenative coupling of POSS-silanols with hydrosilanes. What is more, the reactions of dihydrosilanes led exclusively to silsesquioxanes bearing SiH C


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Inorganic Chemistry Table 3. One-Pot Synthesis of Functionalized Silsesquioxanes Mediated by Ru3(CO)12a

Toluene, argon atmosphere, 120 °C, and 24 h. bIsolated yields of compounds 18−24.

a

Figure 2. Ru-catalyzed one-pot synthesis of functionalized SQs.

functionalities. These hydride-terminated SQ cages turned out to be highly useful derivatives for the synthesis of more functionalized organosilicon compounds via a one-pot procedure. To the best of our knowledge, this is the first example of

such one-pot synthesis achieved in case of a dehydrogenative coupling involving POSS silanols. Further extensions of the presented solution and related applications are currently being undertaken. D


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Inorganic Chemistry

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Figure 3. Proposed mechanism for Si−O−Si moiety formation via dehydrogenative coupling of hydrosilanes and POSS silanols.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b02645. NMR data and spectra of compounds synthesized in this paper (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Grzegorz Hreczycho: 0000-0002-3606-7114 Funding

This work was supported by the National Science Centre (UMO-2017/27/N/ST5/00091). Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS K.K. acknowledges support from the Foundation for Polish Science (FNP START 2018 Scholarship). REFERENCES

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Ru-Catalyzed Dehydrogenative Silylation of POSS-Silanols with

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