Efficient CO<sub>2</sub> Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex

Tüchler, Michael; Gärtner, Lisa; Fischer, Susanne M.; Boese, A. Daniel; Belaj, Ferdinand; Mösch‐Zanetti, Nadia C.

doi:10.1002/anie.201801800

Cited by 40 publications

(32 citation statements)

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“…A neutral system ( 33 ) similar to that of the Parkin Zn−H was reported by Mösch‐Zanetti et al. in 2018 for CO 2 reduction with trimethoxysilane at room temperature and 1 atm CO 2 (TOF=22.2 h −1 ) . They reasoned that the installation of the electron‐withdrawing tris(thiopyridazinyl)methanide ligand resulted in a more electron‐deficient Zn metal center; thus enabling a higher degree of CO 2 activation and faster overall reaction rate.…”

Section: Main‐group Catalysissupporting

confidence: 76%

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO₂

2019

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Catalytic hydrosilylation of carbon dioxide has emerged as a promising approach for carbon dioxide utilization. It allows the reductive transformation of carbon dioxide into value‐added products at the levels of formate, formaldehyde, methanol, and methane. Tremendous progress has been made in the area of carbon dioxide hydrosilylation since the first reports in 1981. This focus review describes recent advances in the design and catalytic performance of leading catalyst systems, including transition‐metal, main‐group, and transition‐metal/main‐group and main‐group/main‐group tandem catalysts. Emphasis is placed on discussions of key mechanistic features of these systems and efforts towards the development of more selective, efficient, and sustainable carbon dioxide hydrosilylation processes.

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Section: Main‐group Catalysissupporting

confidence: 76%

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO₂

2019

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“…However, this catalytic system requires long reaction time (60 h) and a catalyst loading of 6–7 mol % . In this context, Mösch‐Zanetti and collaborators have recently reported that the complex [Zn(H)(Tntm)] ( 18 ) (Tntm=tris(6‐tert‐butyl‐3‐thiopyridazinyl)methanide) catalyzes the hydrosilylation of CO 2 (1 bar) with HSi(OMe) 3 in C 6 D 6 under mild reaction conditions to afford the corresponding silylformate in 99 % yield in 4.5 (298 K) or 2 h (318 K) …”

Section: Catalytic Reaction Of Carbon Dioxide With Silicon Hydridesmentioning

confidence: 99%

Homogeneous Catalytic Reduction of CO₂ with Silicon‐Hydrides, State of the Art

Fernández-Álvarez

Oro

2018

ChemCatChem

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During recent years, the catalytic transformation of CO 2 using silicon-hydrides as reductants has emerged as a promising methodology that allows the selective reduction of CO 2 to the formate, formaldehyde, methoxide or methane level under mild reaction conditions. Moreover, some catalysts have been employed for the formylation and/or methylation of the NÀH bonds of secondary and/or primary amines by their reaction with CO 2 and hydrosilanes. This work summarizes the different catalytic systems that have shown to be efficient for the abovementioned reactions. Furthermore, a brief description of the reactions performance and the conditions employed in each case is included.[a] Dr. ReviewsScheme 12. Complex RuÀS (21)-catalyzed CO 2 -reduction with HSiEt 3 to the bis(silyl)acetal level.Scheme 13. [Ni(PBP)]-catalyzed CO 2 -reduction with hydrosilanes to the bis (silyl)acetal level.Scheme 14. Reaction of [Sc(RCO 2 )(AbP t Bu 2 )] (26) with B(C 6 F 5 ) 3 . Ar= 3,5-ditertbutylphenyl, R=CH 2 SiMe 2 Ph.Scheme 15. CO 2 -reduction with HSiPh 3 to the bis(silyl)acetal level catalyzed by ion pairs 30 (0.5 mol % + 2.0 mol % of B(C 6 F 5 ) 3 ) and 31 (2.0 mol % + 8.0 mol % of B(C 6 F 5 ) 3 ).Scheme 16. CO 2 -reduction with HSiEt 3 to the bis(silyl)acetal level catalyzed by the N,P-heterocyclic germylene-B(C 6 F 5 ) 3 adduct (34).

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“…With zinc, a boratrane complex is not feasible, as boratrane complexes may be formed by reaction of a borate ligand and a metal salt under reduction of the metal which is not an option with zinc. On the other hand, tris(thiopyridazinyl) scorpionate ligands, in which the borate backbone is replaced by carbon, allow the preparation of various mononuclear zinc complexes with a direct zinc carbon bond [21,22]. Furthermore, we previously have observed that the hybrid thiopyridazine-methimazole scorpionate ligand forms a bridging, dinuclear species [23].…”

Section: Introductionmentioning

confidence: 99%

Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands

et al. 2019

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Scorpionate ligands with three soft sulfur donor sites have become very important in coordination chemistry. Despite its ability to form highly electrophilic species, electron-deficient thiopyridazines have rarely been used, whereas the chemistry of electron-rich thioheterocycles has been explored rather intensively. Here, the unusual chemical behavior of a thiopyridazine (6-tert-butylpyridazine-3-thione, HtBuPn) based scorpionate ligand towards zinc is reported. Thus, the reaction of zinc halides with tris(6-tert-butyl-3-thiopyridazinyl)borate Na[TntBu] leads to the formation of discrete torus-shaped hexameric zinc complexes [TntBuZnX]6 (X = Br, I) with uncommonly long zinc halide bonds. In contrast, reaction of the sterically more demanding ligand K[TnMe,tBu] leads to decomposition, forming Zn(HPnMe,tBu)2X2 (X = Br, I). The latter can be prepared independently by reaction of the respective zinc halides and two equiv of HPnMe,tBu. The bromide compound was used as precursor which further reacts with K[TnMe,tBu] forming the mononuclear complex [TnMe,tBu]ZnBr(HPnMe,tBu). The molecular structures of all compounds were elucidated by single-crystal X-ray diffraction analysis. Characterization in solution was performed by means of 1H, 13C and DOSY NMR spectroscopy which revealed the hexameric constitution of [TntBuZnBr]6 to be predominant. In contrast, [TnMe,tBu]ZnBr(HPnMe,tBu) was found to be dynamic in solution.

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Efficient CO₂ Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex

Cited by 40 publications

References 36 publications

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO₂

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO₂

Homogeneous Catalytic Reduction of CO₂ with Silicon‐Hydrides, State of the Art

Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands

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Efficient CO2 Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex

Cited by 40 publications

References 36 publications

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO2

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO2

Homogeneous Catalytic Reduction of CO2 with Silicon‐Hydrides, State of the Art

Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands

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Efficient CO₂ Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO₂

Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO₂

Homogeneous Catalytic Reduction of CO₂ with Silicon‐Hydrides, State of the Art