Access to germasiloxanes and alkynylgermanes mediated by earth | Shijiazhuang AgilePeak Ventures Co.,Ltd

Scientific Reports volume 13, Article number: 5618 (2023) Cite this article

790 Accesses

2 Citations

3 Altmetric

Metrics details

The reactions between silanols or terminal acetylenes with alkynylgermanes have been accomplished using potassium bis(trimethylsilyl)amide as the catalyst. This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such as KOH can serve as efficient catalysts in this process.

Organogermanium compounds are much less studied than their silicon counterparts, but very recently, an impetus to design new synthetic routes to various organogermanes was witnessed and significant contributions were reported1,2,3,4,5,6,7,8,9,10,11. That is not merely a scientific curiosity but primarily, the unique features of germanium compounds are the leading cause of this trend. Moreover, due to their high stability and low toxicity, they can be considered very useful reagents in the synthesis of complex organic molecules4,12. The germanium analogues of siloxanes with Ge–O–Si fragments attract considerable attention owing to their high refractive index, low dielectric constant, and biocompatible properties13,14,15. This may lead to completely new materials with different properties than their silicon analogs16. There are known several available reaction manifolds to forge Ge–O–Si moieties (Fig. 1). They can be readily accessed via well-developed stoichiometric methods. Here, the germasiloxanes are formed by the condensation of chlorogermanes (or aminogermanes) with silanols or metal silanolates17,18. Moreover, there is also a known reaction between germoxanes and silyl azides19. Because of the inconvenient nature of these processes (e.g., high moisture sensitivity of substrates, generation of corrosive or explosive byproducts, etc.), researchers have tried to develop catalytic alternatives. These methods can be generally divided into approaches involving siloxymethylamines20 (or germyl intermediates14), as well as the reaction of various organosilicons with different germylation agents via dehydrogenative21, dealkylative21, and dealkenative22,23,24,25,26,27 coupling reactions. Despite several advantages, other features of these processes, especially the need for an expensive catalyst (e.g., [Ru3(CO)12], Sc(OTf)3, B(C6F5)3, etc.) dramatically reduce their potential. On the other hand, unlike alkynylsilanes, alkynylgermanes have just begun to meet the criteria of useful reagents in organic synthesis. Here, the synthetic arsenal for the formation of sp C–Ge bonds mainly relies on the stoichiometric reaction between moisture-sensitive halogermanes with metal acetylides or the use of expensive transition metal complexes (Ru—vinylgermanes/alkynylgermanes28,29,30, Ir—chlorogermanes/iodo-germanes31,32). Very recently, an outstanding B(C6F5)3-catalyzed cross-dehydrogenative germylation of terminal alkynes with triethylgermanium hydride was reported by the Schoenebeck group33. Considering the drawbacks of previously established methods (e.g., expensive catalysts, the limited availability of hydrogermanes, etc.), it would be fascinating and yet challenging to develop a novel catalytic approach in a more green and sustainable manner. Finally, terminal alkynes can be C–germylated by using 1-trimethylsilyl-2-trimethylgermylacetylene molecule under basic conditions34. To the best of our knowledge, there is only one example of such an atypical synthetic strategy. Notably, this strategy is not without its own disadvantages, including the use of fluoride reagents and expensive crown ethers. Moreover, the authors have reported only two products, with low selectivity and yields (less than 50%).

Context of the investigation.

Sustainable and eco-friendly synthetic approaches proceeded by the main-group species have gained recent significant attention35,36,37,38,39,40,41,42,43,44. Thus, we sought the method leading to versatile germanium compounds that blends the high selectivity of TM-mediated approaches with the practicality of a base-promoted protocol. Based on our recent success in activating silylacetylenes under sustainable catalysis45,46,47,48,49, we reasoned that an appropriate catalytic manifold could provide an efficient platform to generate diversified libraries of organogermanes. In this communication, we report on the catalytic O– and sp C–germylation by using potassium bis(trimethylsilylamide) as the catalyst (Fig. 1d).

Our optimization studies (for details, see Table S1 in SI) revealed that utilizing triethyl(ethynyl)germane (2a) as the germylating agent, and KHMDS as the catalyst led to the corresponding germasiloxane 3a. Using a mixture of acetonitrile and tetrahydrofuran as the medium (v/v 10:1), this main-group catalytic combination afforded the desired product in 92% yield. Particularly noteworthy is a very good conversion of silanols in the presence of potassium hydroxide (for details, see Table S2 in SI). However, we decided to continue our work with potassium bis(trimethylsilylamide), due to better conversions and yields of final products. The catalyst-free attempt was also carried out and proved the essential role of the main-group catalysis and confirmed no leaching of the alkali species from the glassware, which could act as potential co-catalysts50,51. The reaction can be also performed under an air atmosphere but gave inferior results. Figure 2 demonstrates a product scope for alkynylgermanes coupling with silanols using KHMDS in MeCN/THF mixture. The desired germasiloxanes (3a-3n) were obtained in each case with a very good isolated yield (85–99%). Conversely, in the presence of bulky isopropyl substituents at the germanium atom, the lower conversion and isolated yield were observed (3o, 51%).

Substrate scope for O-germylation of various silanols.

We were particularly delighted that dialkynylgermanes could be converted to germasiloxanes (3p-3r). In the case of dibutyldiethynylgermane, the reaction can selectively proceed to both mono- and disubstituted products (3q and 3r). This should be treated as another advantage of this germylation method over previously known approaches due to the possibility of further modifications of the untouched ethynyl group (3q). Encouraged by these results, we then investigated the use of alcohols instead of silanols. We were pleased to find that 1-(4-chlorophenyl)ethan-1-ol and isopropanol were successfully germylated under standard conditions (Fig. 2), leading to products 3s and 3t in moderate yields (50–63%). Unfortunately, our attempts to perform analogous S– and N–germylation failed. Benzenethiol and aniline were not reactive even under forcing conditions.

Intrigued by the high efficiency and chemoselectivity of the transformation, we next pursued the development of further applications of our catalytic system. Encouragingly, this strategy enabled the germylation of terminal alkynes. We started to explore the substrate scope with respect to alkynylgermanes, particularly to their self-metathesis reaction (Fig. 3).

Substrate scope for C–germylation of alkynylgermanes.

Thus, except for bulky triisopropyl(ethynyl)germane (4c; 53%), the reaction smoothly proceeded with remaining alkynylgermanes in good to excellent yields (72–95%). Guided by our previous studies45,48,49, we explored the versatility of our dealkynative coupling of 4a (or 4d) employing a representative set of terminal alkynes (Fig. 4). Although the conversion of phenylacetylene (5a) was also seen with triethyl(ethynyl)germane (2a), we later found that isolated yields were significantly lower than for 4a (Fig. 4; footnotes a, b, and c). Notably, the excess of 4a can be recovered via distillation. However, all actions should be performed exclusively under an argon atmosphere. Otherwise, significant amounts of digermoxane byproduct are formed, thus impeding the isolation process (as well as recovery of 4a). With suitable reaction conditions established (Fig. 4; general conditions), we turned toward the examination of the substrate scope. Coupling reactions of phenylacetylenes substituted with an electron-donating group 5b and electron-withdrawing group 5c provided the corresponding alkynylgermanes 6b and 6c in good yields (61–82%), and the parent phenylacetylene 5a reacted equally well (70%). Next, commercial ene-yne derivative 5d also participated effectively in this reaction (6d, 73% yield), while preserving the ene-functionality untouched. Encouraged by these results, we then investigated the use of N-containing acetylenes 5f-5h, which are biorelevant scaffolds. Our strategy enabled the germylation of one pharmaceutical—pargyline (5f), known as an inhibitor of monoamine-oxidase-B (68%). Importantly, the amine moiety in 5g remained during the reaction, confirming again the high chemoselectivity of our approach. Next, we sought to obtain germylated diyne, which can be subsequently used in polymer chemistry. Using our catalytic system, product 6i was afforded (85% yield). Next, unsymmetrical silyl(germyl)- and bis(germyl)acetylenes were obtained in moderate yields (6j and 6k, 54–61%). It should be noted, that in these particular cases, the products were selectively obtained only for bulky substituted silane (6j) or germane (6k). Otherwise, we observed the mixture of symmetrical and unsymmetrical bis-substituted acetylenes. Finally, we also tested our methodology on bis(dimethylphenylgermyl)acetylene (4d), providing the desired products 6l and 6m in very good yields (78–85%). All these examples highlight both the electronic generality of this method and its tolerance for typically existing organic motifs, showcasing the unique robustness and versatility of our strategy.

Substrate scope for C–germylation of terminal alkynes.

Based on our experimental results (for details, see SI) and our previous developments in the case of analogues alkynylsilanes, a plausible catalytic cycle is presented for the O–germylation (Fig. 5; the mechanism for sp C–germylation is shown in Fig. 6). Please note (for details please see SI), that both silanol and triethylethynylgermane can undergo the deprotonation. However, we still suggest that "the silanol activation pathway" is dominant for the O–germylation considering the expected higher acidity of silanols compared to alkynylgermanes. In the case of sp C–germylation, 1H NMR analysis confirmed a deprotonation step (no signal for the acetylenic proton, for details please see SI). Subsequently, it is suggested that formed acetylide reacts with bis(triorganogermyl)acetylene to generate pentacoordinated germanium intermediates. This is followed by the addition of another alkyne molecule with simultaneous liberation of the desired product and triorganogermylacetylene. Notably, the latter can also serve as a germylating agent or undergo a self-metathesis reaction, which finally leads to the evolution of gaseous acetylene in both scenarios. In general, all the previous protocols for the base-catalyzed reactions of analogous silylacetylenes were assuming the intermediacy of hypervalent species. In our specific case, it is also the most probable pathway. Thus, a plausible catalytic cycle is presented in Fig. 6.

Plausible mechanism for the O–germylation.

Plausible mechanism for the sp C–germylation.

In summary, we have reported on a very efficient protocol for catalytic O–H and sp C–H germylation of silanols and terminal alkynes in the presence of main-group species. Here, a commercially available KHMDS enabled a dealkynative coupling with ample scope. Considering the combination of desirable features (e.g., operational simplicity, high chemoselectivity, benign reaction conditions, low cost of the reagents, and their commercial availability, etc.), we believe this reaction system offers new perspectives for the synthesis of valuable organogermanium compounds in a sustainable and green manner. Furthermore, we anticipate that the general design principle utilizing alkynyl-substituted metalloids will lead to new reactions that are difficult to achieve with traditional transformations. Thus, further studies on the scope and synthetic application of this methodology are currently underway in our laboratory.

General Information: Air- and moisture-sensitive reactions were carried out under an argon atmosphere using standard Schlenk techniques or a glove box. Solvents used for all experiments were purchased from Honeyweel or Sigma Aldrich (Merck), dried over calcium hydride (CaH2), and purified by distillation. Tetrahydrofurane was additionally dried over sodium with benzophenone system. All alkali metal compounds (lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide) were purchased in the solid state from Sigma Aldrich (Merck) or StanLab. Additionally, potassium bis(trimethylsilyl)amide was also purchased as a solution in THF from Sigma Aldrich (Merck). Commercially available silanols (e.g., tert-butyldimethylsilanol, tert-butyldiphenylsilanol, tris(tert-butoxy)silanol, triethylsilanol, triisopropylsilanol, triphenylsilanol, etc.) were purchased from Sigma Aldrich (Merck) or AmBeed and used as received. Non-commercially available silanols were prepared by hydrolysis of corresponding chlorosilanes (e.g., chlorotriisobutylsilane, chlorotributylsilane, etc.). Terminal alkynes (e.g., phenylacetylene, 4-ethynylanisole, 4-ethynyl-α,α,α-trifluorotoluene, 1-ethynylcyclohexene, N-methyl-N-propargylbenzylamine, etc.) were purchased from Sigma-Aldrich (Merck) and used as received. Alkynylgermanes (e.g., triethyl(ethynyl)germane, tributyl(ethynyl)germane, ethynyldimethyl(phenyl)germane, ethynyltriisopropylgermane, etc.) were synthesized from corresponding chlorogermanes by well-known procedure using ethynylmagnesium bromide solution in THF (Grignard reagent). The progress of reactions (conversion of alkynylgermane, silanol, alcohol, or alkyne) was monitored by GC chromatography using Bruker Scion 460-GC and Agilent 5977B GC/MSD with Agilent 8860 GC System. The structures of products were determined by NMR spectroscopy and MS spectrometry. The 1H NMR (400 or 600 MHz), 13C NMR (101 or 151 MHz) and 29Si NMR (79 or 119 MHz) spectra were recorded on Bruker Avance III HD NanoBay spectrometer, using chloroform-d1 (CDCl3) or benzene-d6 (C6D6) as the solvents. Deuterated solvents were purchased from respectively Deutero GmbH (CDCl3 99.6 atom% D) and Sigma Aldrich (Merck) (C6D6 99.8 atom% D) and used as received.

The datasets used and/or analyzed during the current study available from the corresponding author on reasonable request.

Bloux, H. et al. Base-mediated radio-iodination of arenes by using organosilane and organogermane as radiolabelling precursors. Chem. Eur. J. https://doi.org/10.1002/chem.202203366 (2023).

Article PubMed Google Scholar

Selmani, A., Schoetz, M. D., Queen, A. E. & Schoenebeck, F. Modularity in the Csp3 space─alkyl germanes as orthogonal molecular handles for chemoselective diversification. ACS Catal. 12, 4833–4839 (2022).

Article CAS Google Scholar

Kreisel, T. et al. Modular generation of (iodinated) polyarenes using triethylgermane as orthogonal masking group. Angew. Chem. Int. Ed. 61, e202201475 (2022).

Article CAS Google Scholar

Dahiya, A. & Schoenebeck, F. Orthogonal and Modular Arylation of Alkynylgermanes. ACS Catal. 12, 8048–8054 (2022).

Article CAS Google Scholar

Nyga, A. et al. Dual-photofunctional organogermanium compound based on donor–acceptor–donor architecture. Chem. Commun. 58, 5889–5892 (2022).

Article CAS Google Scholar

Kuciński, K., Gruszczyński, M. & Hreczycho, G. Ru-catalyzed formation of thiosilanes and selenosilanes using dichalcogenides as a user-friendly alternative to thiols and selenols. ChemCatChem 14, e202200961 (2022).

Article Google Scholar

Katir, N., Haskouri, J. E., Amoros, P. & Kadib, A. E. Cooperative assembly of redistributed arylgermanium-bearing alkoxysilanes in a mesostructured siloxane network. New J. Chem. 46, 15686–15692 (2022).

Article CAS Google Scholar

Luo, Y., Lv, L. & Li, Z. Copper-catalyzed germyl-azidation of alkenes with germanium hydrides and trimethylsilyl azide. Org. Lett. 24, 8052–8056 (2022).

Article CAS PubMed Google Scholar

Arii, H. et al. Synthesis of germacyclic compounds by cyclization and annulation reactions utilizing in situ generated germyl cations. Organometallics 40, 1363–1370 (2021).

Article CAS Google Scholar

Sahoo, M. K., Kim, D., Chang, S. & Park, J.-W. Regioselective access to α-vinylsilanes and α-vinylgermanes by cobalt-catalyzed migratory hydrofunctionalization of 2-alkynes. ACS Catal. 11, 12777–12784 (2021).

Article CAS Google Scholar

Zaranek, M., Nowicki, M., Andruszak, P., Hoffmann, M. & Pawluć, P. Hydrogermylation initiated by trialkylborohydrides: A living anionic mechanism. Chem. Commun. 58, 13979–13982 (2022).

Article CAS Google Scholar

Xu, Q.-H. & Xiao, B. Organogermanium(IV) compounds in photo-induced radical reactions. Org. Chem. Front. 9, 7016–7027 (2022).

Article CAS Google Scholar

Murugavel, R., Voigt, A., Walawalkar, M. G. & Roesky, H. W. Hetero- and metallasiloxanes derived from silanediols, disilanols, silanetriols, and trisilanols. Chem. Rev. 96, 2205–2236 (1996).

Article CAS PubMed Google Scholar

Kamitani, M., Fukumoto, K., Tada, R., Itazaki, M. & Nakazawa, H. Catalytic synthesis of cyclic and linear germoxanes mediated by an iron complex. Organometallics 31, 2957–2960 (2012).

Article CAS Google Scholar

Skoczeń, A. et al. New ceramics precursors containing Si and Ge atoms—cubic germasilsesquioxanes—synthesis, thermal decomposition and spectroscopic analysis. Molecules 27, 1441 (2022).

Article PubMed PubMed Central Google Scholar

Risen Jr, W. M., Wang, Y. Z. & Honore, A. Germanosiloxane materials and optical components comprising the same. U.S. Patent 6248852B1 (2001). Short note: Germasiloxanes may feature with higher or lower refractive indices, as well as varied electrical and optical properties than analogues siloxanes.

Schmidbaur, H. & Hussek, H. Präparative und spektroskopische untersuchungen an alkylgermanosiloxanen. J. Organomet. Chem. 1, 235–243 (1964).

Article CAS Google Scholar

Puff, H., Kök, T. R., Nauroth, P. & Schuh, W. Ein siebengliedriger germanium–silicium–sauerstoff-ring: 1,1,2,2,4,4,6,6-Octaphenyl-1,2-digerma-4,6-disila-3,5,7-trioxa-cycloheptan. J. Organomet. Chem. 281, 141–148 (1985).

Article CAS Google Scholar

Zhou, Q. & Weber, W. P. Exchange reactions between trimethylsilyl azide and hexamethyldigermoxane. J. Organomet. Chem. 342, 291–294 (1988).

Article CAS Google Scholar

Arias-Ugarte, R., Sharma, H. K., Morris, A. L. C. & Pannell, K. H. Metal-catalyzed reduction of HCONR’2, R’ = Me (DMF), et (DEF), by silanes to produce R’2NMe and disiloxanes: A mechanism unraveled. J. Am. Chem. Soc. 134, 848–851 (2012).

Article CAS PubMed Google Scholar

Ignatovich, L., Muravenko, V., Grinberga, S. & Lukevics, E. Novel reactions to form an Si–O–Ge group. Chem. Heterocycl. Compd. 42, 268–271 (2006).

Article CAS Google Scholar

Hreczycho, G., Frąckowiak, D., Pawluć, P. & Marciniec, B. A new catalytic approach to germasiloxanes. Tetrahedron Lett. 52, 74–76 (2011).

Article CAS Google Scholar

Hreczycho, G., Pawluć, P. & Marciniec, B. A new selective approach to unsymmetrical siloxanes and germasiloxanes via O-metalation of silanols with 2-methylallylsilanes and 2-methylallylgermanes. New J. Chem. 35, 2743–2746 (2011).

Article CAS Google Scholar

Hreczycho, G., Kuciński, K., Pawluć, P. & Marciniec, B. Catalytic synthesis of linear oligosiloxanes and germasiloxanes mediated by scandium trifluoromethanesulfonate. Organometallics 32, 5001–5004 (2013).

Article CAS Google Scholar

Kaźmierczak, J. & Hreczycho, G. Catalytic approach to germanium-functionalized silsesquioxanes and germasilsesquioxanes. Organometallics 36, 3854–3859 (2017).

Article Google Scholar

Kaźmierczak, J. & Hreczycho, G. Nafion as effective and selective heterogeneous catalytic system in O-metalation of silanols and POSS silanols. J. Catal. 367, 95–103 (2018).

Article Google Scholar

Kuciński, K. & Hreczycho, G. O-Metalation of silanols and POSS silanols over Amberlyst-15 catalyst: A facile route to unsymmetrical siloxanes, borasiloxanes and germasiloxanes. Inorg. Chim. Acta 490, 261–266 (2019).

Article Google Scholar

Marciniec, B., Ławicka, H. & Dudziec, B. New catalytic route to alkynylgermanes. Organometallics 26, 5188–5192 (2007).

Article CAS Google Scholar

Marciniec, B., Ławicka, H. & Dudziec, B. A new catalytic route to synthesis of silylgermylethynes. J. Organomet. Chem. 693, 235–240 (2008).

Article CAS Google Scholar

Rzonsowska, M., Dudziec, B. & Marciniec, B. Synthesis of a new class of silsesquioxanes with alkynyl and germyl functionality. Dalton Trans. 45, 17187–17194 (2016).

Article CAS PubMed Google Scholar

Rzonsowska, M., Kownacki, I., Dudziec, B. & Marciniec, B. Iridium complex catalyzed germylative coupling reaction between alkynes and iodogermanes—a new route to alkynylgermanium and alkynylgermasilicon compounds. Dalton Trans. 43, 16795–16799 (2014).

Article CAS PubMed Google Scholar

Rzonsowska, M. et al. A simple catalytic route for alkynylgermanes. Eur. J. Inorg. Chem. 2016, 339–346 (2016).

Article CAS Google Scholar

Dahiya, A. & Schoenebeck, F. Direct C–H dehydrogenative germylation of terminal alkynes with hydrogermanes. Org. Lett. 24, 2728–2732 (2022).

Article CAS PubMed Google Scholar

Lukevics, E. et al. Fluoride ion mediated reactions of disubstituted acetylenes Me3SiC≡CMMe3 (M=C, Si, Ge, Sn) with terminal acetylenes. J. Organometal. Chem. 634, 69–73 (2001).

Article CAS Google Scholar

Leitao, E. M., Jurca, T. & Manners, I. Catalysis in service of main group chemistry offers a versatile approach to p-block molecules and materials. Nature Chem. 5, 817–829 (2013).

Article ADS CAS Google Scholar

Melen, R. L. Dehydrocoupling routes to element–element bonds catalysed by main group compounds. Chem. Soc. Rev. 45, 775–788 (2016).

Article CAS PubMed Google Scholar

Luo, C. & Bandar, J. S. Selective Defluoroallylation of trifluoromethylarenes. J. Am. Chem. Soc. 141, 14120–14125 (2019).

Article CAS PubMed Google Scholar

Kuciński, K. & Hreczycho, G. Hydrosilylation and hydroboration in a sustainable manner: From earth-abundant catalysts to catalyst-free solutions. Green Chem. 22, 5210–5224 (2020).

Article Google Scholar

Roy, M. M. D. et al. Molecular main group metal hydrides. Chem. Rev. 121, 12784–12965 (2021).

Article CAS PubMed Google Scholar

Reidl, T. W. & Bandar, J. S. Lewis basic salt-promoted organosilane coupling reactions with aromatic electrophiles. J. Am. Chem. Soc. 143, 11939–11945 (2021).

Article CAS PubMed PubMed Central Google Scholar

Puleo, T. R., Sujansky, S. J., Wright, S. E. & Bandar, J. S. Organic superbases in recent synthetic methodology research. Chem. Eur. J. 27, 4216–4229 (2021).

Article CAS PubMed Google Scholar

Gao, H., Battley, A. & Leitao, E. M. The ultimate Lewis acid catalyst: Using tris(pentafluorophenyl) borane to create bespoke siloxane architectures. Chem. Commun. 58, 7451–7465 (2022).

Article CAS Google Scholar

Kuciński, K., Stachowiak-Dłużyńska, H. & Hreczycho, G. Catalytic silylation of O–nucleophiles via Si–H or Si–C bond cleavage: A route to silyl ethers, silanols and siloxanes. Coord. Chem. Rev. 459, 214456 (2022).

Article Google Scholar

Wright, S. E. & Bandar, J. S. A base-promoted reductive coupling platform for the divergent defluorofunctionalization of trifluoromethylarenes. J. Am. Chem. Soc. 144, 13032–13038 (2022).

Article CAS PubMed Google Scholar

Kuciński, K., Stachowiak, H. & Hreczycho, G. Silylation of alcohols, phenols, and silanols with alkynylsilanes—an efficient route to silyl ethers and unsymmetrical siloxanes. Eur. J. Org. Chem. 2020, 4042–4049 (2020).

Article Google Scholar

Stachowiak, H., Kuciński, K., Kallmeier, F., Kempe, R. & Hreczycho, G. Cobalt-catalyzed dehydrogenative C−H silylation of Alkynylsilanes. Chem. Eur. J. 28, e202103629 (2022).

Article CAS PubMed Google Scholar

Lewandowski, D., Cytlak, T., Kempe, R. & Hreczycho, G. Ligand-controlled cobalt-catalyzed formation of carbon-boron bonds: Hydroboration vs C-H/B–H dehydrocoupling. J. Catal. 413, 728–734 (2022).

Article CAS Google Scholar

Kuciński, K. & Hreczycho, G. Transition metal-free catalytic C−H silylation of terminal alkynes with bis(trimethylsilyl)acetylene initiated by KHMDS. ChemCatChem 14, e202200794 (2022).

Article Google Scholar

Kuciński, K. & Hreczycho, G. Silicon-nitrogen bond formation via dealkynative coupling of amines with bis(trimethylsilyl)acetylene mediated by KHMDS. Chem. Commun. 58, 11386–11389 (2022).

Article Google Scholar

Pentsak, E. O., Eremin, D. B., Gordeev, E. G. & Ananikov, V. P. Phantom reactivity in organic and catalytic reactions as a consequence of microscale destruction and contamination-trapping effects of magnetic stir bars. ACS Catal. 9, 3070–3081 (2019).

Article CAS Google Scholar

Sau, S., Pramanik, M., Bal, A. & Mal, P. Reported catalytic hydrofunctionalizations that proceed in the absence of catalysts: The importance of control experiments. Chem. Rec. 22, e202100208 (2022).

Article CAS PubMed Google Scholar

Download references

This work was supported by the Adam Mickiewicz University in Poznań (KK-ID-UB project no. 038/04/NŚ/0001; HS-ID-UB project no. 017/02/SNS/0009), and by grant no. POWR.03.02.00-00-I020/17 (HS) co-financed by the European Union through the European Social Fund under the Operational Program Knowledge Education Development. This work was also supported by a National Science Centre Grant UMO-2018/30/E/ST5/00045 (GH).

Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego St. 8, 61-614, Poznan, Poland

Hanna Stachowiak-Dłużyńska, Krzysztof Kuciński, Konstancja Broniarz, Ewelina Szafoni, Marcin Gruszczyński, Dariusz Lewandowski & Grzegorz Hreczycho

Dipartimento di Scienze Chimiche, Università degli studi di Catania, viale A. Doria 6, 95125, Catania, Italy

Giuseppe Consiglio

You can also search for this author in PubMed Google Scholar

Methodology, K.K, G.H; Synthesis of Germasiloxanes, H. S.-D., K.K.; Synthesis of Starting Materials—Silanols, E. S.; Synthesis of Starting Materials—Alkynylgermanes, K.B., H. S.-D.; Synthesis of Products—Alkynylgermanes, H. S.-D., M. G., and D. L.; Formal analysis, H. S.-D., K.K., K. B., E. S., M. G., and D. L.; writing—original draft preparation, K.K. and H. S.-D.; visualization, K.K.; supervision, K.K., G.C., and G.H.; funding acquisition, H. S.-D., K.K., and G.H. All authors reviewed the manuscript.

Correspondence to Krzysztof Kuciński or Grzegorz Hreczycho.

The authors declare no competing interests.

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

Stachowiak-Dłużyńska, H., Kuciński, K., Broniarz, K. et al. Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species. Sci Rep 13, 5618 (2023). https://doi.org/10.1038/s41598-023-32172-9

Download citation

Received: 31 January 2023

Accepted: 23 March 2023

Published: 06 April 2023

DOI: https://doi.org/10.1038/s41598-023-32172-9

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.