Synthesis of Poly(silyl ethers) via Iridium-Catalyzed Dehydrocoupling Polymerization

Zhai, Xiao-Yong; Hu, Shu-Bo; Shi, Lei; Zhou, Yong‐Gui

doi:10.1021/acs.organomet.8b00316

Cited by 15 publications

(6 citation statements)

References 51 publications

(38 reference statements)

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“…Alkoxysilanes can also be obtained by the catalytic dehydrocoupling of PhSiH 3 and alcohols, a class of reaction that is of interest because it releases H 2 on demand and is thereby of relevance to the “hydrogen economy”. , For example, (Nitron NHC )Ir(CO) 2 Cl serves as a catalyst for the rapid formation of a 1.5:1 mixture of PhSiH(OCH 2 Ph) 2 and PhSi(OCH 2 Ph) 3 via the room-temperature dehydrocoupling of PhSiH 3 and PhCH 2 OH, with TOF > 320 h –1 per Si–H bond, followed by the complete conversion to PhSi(OCH 2 Ph) 3 over a period of 1 day (Scheme ). Dehydrocoupling of Ph 2 SiH 2 with PhCH 2 OH immediately affords the mono-alkoxide Ph 2 SiH(OCH 2 Ph), while conversion to the bis-alkoxide Ph 2 Si(OCH 2 Ph) 2 occurs over a period of several days at room temperature.…”

Section: Results and Discussionmentioning

confidence: 99%

N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties

et al. 2021

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The mesoionic compound (1,4-diphenyl-1,2,4-triazol-4-ium-3-yl)phenylazanide, commonly referred to as Nitron, has been employed as a "crypto-NHC" to afford 1,2,4-triazolylidene compounds of nickel, palladium, and iridium. Specifically, Nitron reacts with NiBr 2 , PdCl 2 , and [Ir(COD)Cl] 2 to afford the Nheterocyclic carbene complexes (Nitron NHC ) 2 NiBr 2 , (Nitron NHC ) 2 PdCl 2 , and (Nitron NHC )Ir(COD)Cl, respectively. The lattermost compound reacts with (i) CO to afford the dicarbonyl compound (Nitron NHC )Ir(CO) 2 Cl and (ii) CO, in the presence of PPh 3 , to afford the monocarbonyl compound (Nitron NHC )Ir(PPh 3 )-(CO)Cl. Structural studies on (Nitron NHC )Ir(COD)Cl and (Nitron NHC )Ir(CO) 2 Cl indicate that Nitron NHC has a stronger trans influence than does Cl; furthermore, IR spectroscopic studies on (Nitron NHC )Ir(CO) 2 Cl indicate that Nitron NHC is electronically similar to the structurally related Enders carbene but is less electron donating than imidazol-2-ylidenes with aryl substituents. Significantly, the Nitron NHC ligand affords catalytic systems, as illustrated by the ability of (Nitron NHC )Ir(CO) 2 Cl to effect (i) the dehydrogenation of formic acid, (ii) aldehyde hydrosilylation, (iii) dehydrocoupling of hydrosilanes and alcohols, and (iv) ketone reduction via transfer hydrogenation.

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Section: Results and Discussionmentioning

confidence: 99%

N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties

et al. 2021

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“…They are widely used as oils, rubbers, silicone resins, heat-resistant materials and optoelectronic materials, because of their excellent thermal, electronic and optical properties. [23][24][25][26] Progress has been made towards the application of organocatalytic step-growth polymerizations in the synthesis of organosilicon polymers, with such reactions including dehydrogenative coupling, [27][28][29][30][31][32] hydrosilylation of silanes with ketones, alkenes or alkynes, [33][34][35][36][37] the Piers-Rubinsztajn reaction 38,39 and others. 40,41 Using the indole skeleton to construct polymeric materials has also attracted intense attention.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of fluorescent poly(silyl indole)s via borane-catalyzed C–H silylation of indoles

Zhang

Han

et al. 2023

Polym. Chem.

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“…Among these, transition metal-catalyzed polymerization has attracted significant interest in the recent past. [15] Precious transition metal complexes derived from rhodium, iridium, palladium, and platinum catalyze the dehydrogenative polymerization of silanes and diols to produce PSE's with hydrogen as the only byproduct. [16,17,18] On the contrary, ironcatalyzed dehydrogenative polymerization of silanes and diols to produce PSEs has been scarcely attempted.…”

Section: Introductionmentioning

confidence: 99%

Iron‐Catalyzed Alkoxylation, Dehydrogenative‐Polymerization and Tandem Hydrosilylative‐Alkoxylation

Sen

Kumar

Tewari

et al. 2023

Chemistry A European J

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Alkoxylation, hydrosilylative-alkoxylation, and dehydrogenative-polymerization are some of the most widely used transformations in synthetic chemistry. However, these transformations are traditionally catalyzed by precious, and rare late-transition metals. Presented here is a molecularly defined iron complex that catalyzes alkoxylation, tandem hydrosilylative-alkoxylation, and dehydrogenative polymerization of silanes under mild conditions. The iron complex [Fe(CO) 4 (H)(SiPh 3 )] 1 catalyzes a direct SiÀ O coupling reaction between an array of silanes and alcohols to produce desired alkoxysilanes in excellent yield, with H 2 as the only byproduct.The iron catalyst tolerates various functional groups and provides access to 20 alkoxysilanes, including essential molecules such as β-citronellol and cholesterol. Further, complex 1 catalyzes the polymerization of renewable diol and silane monomer to produce a renewable and degradable poly(isosorbideÀ silyl ether). Remarkably, complex 1 catalyzes a tandem hydrosilylative-alkoxylation of alkynes under mild conditions to yield unsaturated silyl ethers. The synthetic utility has been demonstrated by gram-scale alkoxylation and hydrosilylative-alkoxylation reactions.

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Synthesis of Poly(silyl ethers) via Iridium-Catalyzed Dehydrocoupling Polymerization

Cited by 15 publications

References 51 publications

N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties

N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties

Synthesis of fluorescent poly(silyl indole)s via borane-catalyzed C–H silylation of indoles

Iron‐Catalyzed Alkoxylation, Dehydrogenative‐Polymerization and Tandem Hydrosilylative‐Alkoxylation

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