Compounds with Bonds between Silicon and d-Block Metal Atoms

Housecroft, Catherine E.

doi:10.1016/b0-08-045047-4/00205-3

Cited by 4 publications

(5 citation statements)

References 347 publications

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“…It should be noted, however, that a stronger *CO adsorption should yield a significant redshift in the ν(C�O) vibrational frequency. 67,68 At more negative potentials, the strong coverage and electric field effects on the *CO atop band position make it difficult to make any conclusions on the *CO adsorption strength even though the *CO band of the anodized film is redshifted compared with the as-prepared film at −0.7 V to −1 V. On the other hand, since the *CO atop band of the anodized Cu thin film was slightly blueshifted by 1.9 cm −1 (Figure 2d) compared to the as-prepared Cu film at −0.35 V (where coverage and electric field effects on the vibrational frequency are assumed to be minimal), the *CO binding can be inferred to be marginally weaker for the anodized film, as we further analyzed via DFT in the succeeding sections. Therefore, the faster growth of the *CO atop band on the anodized Cu film is more likely caused by the accessible adsorption sites on defects produced during the reduction of the copper oxide thin film instead of a stronger *CO binding strength.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper

Delmo,

Wang,

Song

et al. 2024

J. Am. Chem. Soc.

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The reaction mechanism of CO 2 electroreduction on oxide-derived copper has not yet been unraveled even though high C 2+ Faradaic efficiencies are commonly observed on these surfaces. In this study, we aim to explore the effects of copper anodization on the adsorption of various CO 2 RR intermediates using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) on metallic and mildly anodized copper thin films. The in situ SEIRAS results show that the preoxidation process can significantly improve the overall CO 2 reduction activity by (1) enhancing CO 2 activation, (2) increasing CO uptake, and (3) promoting C−C coupling. First, the strong *COO − redshift indicates that the preoxidation process significantly enhances the first elementary step of CO 2 adsorption and activation. The rapid uptake of adsorbed *CO atop also illustrates how a high *CO coverage can be achieved in oxide-derived copper electrocatalysts. Finally, for the first time, we observed the formation of the *COCHO dimer on the anodized copper thin film. Using DFT calculations, we show how the presence of subsurface oxygen within the Cu lattice can improve the thermodynamics of C 2 product formation via the coupling of adsorbed *CO and *CHO intermediates. This study advances our understanding of the role of surface and subsurface conditions in improving the catalytic reaction kinetics and product selectivity of CO 2 reduction.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper

Delmo,

Wang,

Song

et al. 2024

J. Am. Chem. Soc.

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“…The inherent reactivity of the C−N bond in these isocyano ligands could be considered an impediment to further explore their interaction with other reagents. 127 Interesting reactivity was also observed for the zerovalent tetraisocyanide complex Co(CNAr Mes2 ) 4 (88), which undergoes L-type ligand substitution or exhibits (metallo)radical behavior. Both types of reactivity were explored by Figueroa and co-workers.…”

Section: 2]cryptand)][c 60mentioning

confidence: 99%

“…The carbonyl ligand (CO) is among the most studied types of ligands in organometallic chemistry . Upon coordination to a metal center, carbon monoxide behaves as a weak σ-donor and as a strong π-acceptor (strong π-acid).…”

Section: Synthesis and Basic Reactivity Patterns Of D-block Metalatesmentioning

confidence: 99%

“…The carbonyl ligand (CO) is among the most studied types of ligands in organometallic chemistry. 88 Upon coordination to a metal center, carbon monoxide behaves as a weak σ-donor and as a strong π-acceptor (strong π-acid). In fact, carbonyl ligands are very effective in stabilizing highly reduced metal centers and metals in uncommon oxidation states since they can accept the excess electron density through M−CO πbackbonding (Figure 2).…”

Section: Complexes Containing Carbonyl Ligandsmentioning

confidence: 99%

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Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Landaeta,

Horsley Downie,

Wolf

2024

Chem. Rev.

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This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident. Consequently, exciting applications in small molecule activation have been developed, including in catalytic transformations. This article intends to guide the reader through the fascinating world of low-valent transition metalates. The first part of the review describes the synthesis and reactivity of d-block metalates stabilized by an assortment of ligand frameworks, including carbonyls, isocyanides, alkenes and polyarenes, phosphines and phosphorus heterocycles, amides, and redox-active nitrogen-based ligands. Thereby, the reader will be familiarized with the impact of different ligand types on the physical and chemical properties of metalates. In addition, ion-pairing interactions and metal−metal bonding may have a dramatic influence on metalate structures and reactivities. The complex ramifications of these effects are examined in a separate section. The second part of the review is devoted to the reactivity of the metalates toward small inorganic molecules such as H 2 , N 2 , CO, CO 2 , P 4 and related species. It is shown that the use of highly electron-rich and reactive metalates in small molecule activation translates into impressive catalytic properties in the hydrogenation of organic molecules and the reduction of N 2 , CO, and CO 2 . The results discussed in this review illustrate that the potential of transition metalate anions is increasingly being tapped for challenging catalytic processes with relevance to organic synthesis and energy conversion. Therefore, it is hoped that this review will serve as a useful resource to inspire further developments in this dynamic research field.

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“…Organotin compounds can be separated from inorganic tin by changing the chloride counterions of the OTCs to fluorides. In this case, low-dissociation complex compounds of the OTCs are formed [41,42], while inorganic tin (IV) halides remain in the water [14]. These properties of OTCs were considered when they were precipitated from aqueous solutions with potassium fluoride or iodide.…”

Section: Separation Of Inorganic and Organic Tin In Watermentioning

confidence: 99%

Possibilities and Limitations of ICP-Spectrometric Determination of the Total Content of Tin and Its Inorganic and Organic Speciations in Waters with Different Salinity Levels—Part 2: Separate Determination of Inorganic and Organic Speciations of Tin

Temerdashev,

Abakumov,

Bolshov

et al. 2023

Molecules

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In this study, determination of the inorganic and organic forms of tin in waters of different salinities is considered. The possibility of the separation of speciations of tin using liquid–liquid extraction (LLE); precipitation with fluorides, iodides, ammonia, and iron (III) chloride; and sorption of organotin compounds (OTCs) was studied. The LLE and analyte precipitation methods proved to be ineffective. Inorganic and organic forms of tin were separated by the sorption of OTCs using silica gel sorbent Diapak C18. Under optimized conditions, a technique for the separate determination of the forms of tin in natural waters was developed. The technique combines hydride generation and microwave mineralization of solutions followed by ICP spectrometry. The inorganic forms of tin were determined after their solid-phase separation from organotin compounds. The lower limits of analyte quantification were 0.03 μg/L (ICP-MS) and 0.05 μg/L (ICP-OES), which provide separate determinations of inorganic and organic forms of tin in waters with different salinities. The content of OTCs in water was determined by subtracting the inorganic concentration from the total concentration of tin. The technique will allow a comprehensive assessment of the toxicological impact of tin speciations on the aquatic ecosystem.

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Compounds with Bonds between Silicon and d-Block Metal Atoms

Cited by 4 publications

References 347 publications

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Possibilities and Limitations of ICP-Spectrometric Determination of the Total Content of Tin and Its Inorganic and Organic Speciations in Waters with Different Salinity Levels—Part 2: Separate Determination of Inorganic and Organic Speciations of Tin

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Compounds with Bonds between Silicon and d-Block Metal Atoms

Cited by 4 publications

References 347 publications

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO2 Reduction and C–C Coupling on Oxide-Derived Copper

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO2 Reduction and C–C Coupling on Oxide-Derived Copper

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Possibilities and Limitations of ICP-Spectrometric Determination of the Total Content of Tin and Its Inorganic and Organic Speciations in Waters with Different Salinity Levels—Part 2: Separate Determination of Inorganic and Organic Speciations of Tin

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In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO₂ Reduction and C–C Coupling on Oxide-Derived Copper