Redox-Active Heterometallic Ferrocenylalkynyl Carbosilane Dendrimers Incorporating Os<sub>3</sub>(CO)<sub>10</sub> Clusters

Nievas, Ángel; Medel, María; Hernández, Ernesto Sánchez; Delgado, Esther; Martı́n, Avelino; Casado, Carmen M.; Alonso, Beatriz

doi:10.1021/om100537k

Cited by 15 publications

(5 citation statements)

References 63 publications

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“…A series of aryl‐ and heteroarylacetylenes with different electronic and steric natures participated in this strategy successfully ( 3l – 3p ). Metallosilylacetylene 3q , which is potentially useful as a key component for optoelectronic materials,16 was synthesized in an excellent yield. As shown thus far, the outstanding tolerance of the functional groups, Cl, OCOMe, phthalimidoyl, HexO CH 2 CC, CN, t‐ Bu(Me) 2 SiO, CC, CF 3 and ferrocenyl, is noteworthy.…”

Section: Lewis Acid‐catalyzed Dehydrogenative Silylation Of 1‐octyne mentioning

confidence: 99%

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

et al. 2012

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Section: Lewis Acid‐catalyzed Dehydrogenative Silylation Of 1‐octyne mentioning

confidence: 99%

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

et al. 2012

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“…Shortly thereafter, Rosenblum and co-workers reported a further improvement to this synthesis by treating acetylferrocene with phosphorus(V) oxychloride in dimethylformamide . This functionalized metallocene is a useful starting material, not only for the synthesis of its homopolymer, poly(ethynylferrocene), − but also for a wide variety of more complex organometallic derivatives, such as ferrocenyl dendrimers, − dendronized polymers, and heterometallic molecules . Likewise, ethynylferrocene has been used as a starting compound for the preparation of bioorganometallic steroidal androgen derivatives …”

Section: Introductionmentioning

confidence: 99%

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

et al. 2014

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The application of ethynylferrocene, FcCCH (1), as a highly efficient electroactive precursor for the thiol–yne click reaction is presented. For this purpose, a wide range of functionalized thiols, namely 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic acid, 4-aminothiophenol, and benzene-1,3-dithiol as well as tetrathiol pentaerythritol tetrakis(3-mercaptopropionate), were investigated. This facile thiol–ethynylferrocene radical reaction has resulted in the quantitative formation and isolation of the newly ferrocenyl–vinyl sulfides FcCHCHS(CH2)2OH (2 Z and 2 E ), FcCHCHSCH2CH(OH)CH2OH (3 Z and 3 E ), FcCHCHS(CH2)2COOH (4 Z and 4 E ), FcC(CH2)S(1,4-C6H4)NH2 (5α), FcCHCHS(1,3-C6H4)SCHCHFc (6), and [FcCHCHS(CH2)2COOCH2]4C (7). Thiol–ethynylferrocene reactions have been initiated either by heat, in toluene with AIBN, or by UV light irradiation in THF in the presence of DMPA as photoinitiator. The outcome of the hydrothiolation of ethynylferrocene strongly depends on the thiol structure and on the initiation method employed. A simple mixing of metallocene 1 with the thiol HS(CH2)2OH or HS(CH2)2COOH in a proper ratio, in THF at 20 °C, in a initiator-free thiol–yne reaction, causes hydrothiolation of 1 to occur, allowing for the formation of vinyl sulfides 2 Z , 2 E and 4 Z , 4 E in good isolated yields. In contrast to the bis-addition typically observed for thiol–yne reactions, no double hydrothiolation to FcCCH has been observed for any of the thiols under any conditions studied. Electrochemical studies showed that tetrametallic compound 7, containing four sulfur-bridged ferrocenyl–vinyl moieties, behaves as a tetrapodal adsorbate molecule, exhibiting excellent chemisorption properties, and spontaneously forms robustly adsorbed 7 films onto Au or Pt electrode surfaces.

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“…The heteroarylacetylene also reacted well with HSi(OEt) 3 , affording the desired product 4pa in 87% yield. Moreover, metallosilylacetylene 4qa , an important compound having a potential application in optoelectronic materials, was obtained in 95% yield in this reaction. Three different naphthalenylacetylenes could also be silylated efficiently to provide the products in excellent yields under the standard reaction conditions ( 4ra – 4ta ).…”

Section: Results and Discussionmentioning

confidence: 99%

Dehydrogenative Coupling of Terminal Alkynes with O/N-Based Monohydrosilanes Catalyzed by Rare-Earth Metal Complexes

et al. 2020

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Newly synthesized rare-earth metal alkyl complexes bearing a tripyrrolyl ligand act as excellent precatalysts for the cross-dehydrogenative coupling between various terminal alkynes and O/N-based monohydrosilanes of HSi(OEt) 3 /HSi(NMe 2 ) 3 , leading to the formation of a variety of alkoxysilylalkyne and aminosilylalkyne derivatives in good to high yields. The precatalystswere easily prepared in high yields via the reactions of RE(CH 2 SiMe 3 ) 3 (thf) 2 with the proligand H 2 L in a single step. Mechanistic studies reveal that treatment of 1 with phenylacetylene could generate the active catalytic species: dinuclear rare-earth metal alkynides (L(thf) n [RE(μ-CCPh)] 2 L) (RE = Y(5a), n = 1; Yb(5c), n = 0), which could react with HSi(OEt) 3 to produce the coupling product 4aa and the dinuclear rare-earth metal hydrides (L (thf)[RE(μ-H)] 2 L) (RE = Y(6a); Yb(6c)). By contrast, prior treatment of 1c with HSi(OEt) 3 proceeds via cleavage of the Si−O bond to produce the dinuclear ytterbium alkoxide (LYb(μ-OEt)) 2 7c, which is inert in the dehydrogenative coupling reaction. The results of the mechanistic studies are consistent with the observation that the reaction is greatly influenced by the addition sequence of precatalyst/alkynes/silanes.

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Redox-Active Heterometallic Ferrocenylalkynyl Carbosilane Dendrimers Incorporating Os₃(CO)₁₀ Clusters

Abstract: First and second generations of carbosilane heterometallic dendrimers 7−10 have been prepared by reaction of the novel dendrimers 1−4, functionalized with ferrocenylethynyl and ferrocenylbutadiynyl, with Os3(CO)10(NCMe)2.

Cited by 15 publications

References 63 publications

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

Dehydrogenative Coupling of Terminal Alkynes with O/N-Based Monohydrosilanes Catalyzed by Rare-Earth Metal Complexes

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Redox-Active Heterometallic Ferrocenylalkynyl Carbosilane Dendrimers Incorporating Os3(CO)10 Clusters

Abstract: First and second generations of carbosilane heterometallic dendrimers 7−10 have been prepared by reaction of the novel dendrimers 1−4, functionalized with ferrocenylethynyl and ferrocenylbutadiynyl, with Os3(CO)10(NCMe)2.

Cited by 15 publications

References 63 publications

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

Dehydrogenative Coupling of Terminal Alkynes with O/N-Based Monohydrosilanes Catalyzed by Rare-Earth Metal Complexes

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Redox-Active Heterometallic Ferrocenylalkynyl Carbosilane Dendrimers Incorporating Os₃(CO)₁₀ Clusters