Pd Metal Research Articles

Titanium‐Catalyzed Reaction of Silacyclobutanes with Alkenes: Mimicking the Reactivity and Reversing the Selectivity Towards Late Transition Metals

AbstractTransition metal‐catalyzed ring opening and expansion reactions of silacyclobutanes (SCBs) constitute an atom‐ and step‐economical strategy to construct value‐added silicon‐containing chemicals. Despite extensive studies, the reaction of SCBs with simple alkenes has only one precedent. Moreover, most reported reactions of SCBs use late transition metals (Pd, Ni, Rh) as catalysts. By contrast, there are no reports of using early transition metals. Herein, we report the first example, to our knowledge, of early‐transition‐metal‐catalyzed reactions of SCBs using earth's second abundant titanium as a catalyst. Notably, orthogonal selectivity was observed. Selective activation of the relatively inert C(sp3)−Si bond was achieved in the case of benzosilacyclobutenes, a selectivity that has rarely been achieved using other metals. Even for silacyclobutanes with C(sp3)−Si bonds only, our titanium system also shows complementary selectivity towards late transition metals to give distinct products. Thus, structurally varied SCBs and alkenes were reacted in our system to afford structurally diverse silicon‐containing products that are otherwise difficult to obtain using other transition metals.

Nanoporous High Entropy Alloy Al-Pt-Pd-Ru as an Efficient Catalyst for One-Pot Reductive Amination of Nitroarenes.

High entropy alloys (HEAs) are promising heterocatalysts because of their unique physicochemical properties, but research on HEA-catalyzed tandem reactions is lacking. Moreover, limited research on HEAs for molecular transformation has hindered their development. Herein, an unsupported nanoporous HEA Al-Pt-Pd-Ru (HEANPore) prepared using a top-down dealloying method is reported. The Lewis acidity and electron redistribution of the noble metals Pt, Pd, and Ru are identified to be intrinsic of high activity and selectivity of HEANPore in the one-pot reductive amination of nitroarenes. The competitive adsorption of the reactant and corresponding reaction mechanism are investigated using DFT. This study demonstrates the exceptional performance of the HEANPore in tandem reactions, presenting new possibilities for the application of HEAs in the field of catalysis.

Titanium-Catalyzed Reaction of Silacyclobutanes with Alkenes: Mimicking the Reactivity and Reversing the Selectivity Towards Late Transition Metals.

Transition metal-catalyzed ring opening and expansion reactions of silacyclobutanes (SCBs) constitute an atom- and step-economical strategy to construct value-added silicon-containing chemicals. Despite extensive studies, the reaction of SCBs with simple alkenes has only one precedent. Moreover, most reported reactions of SCBs use late transition metals (Pd, Ni, Rh) as catalysts. By contrast, there are no reports of using early transition metals. Herein, we report the first example, to our knowledge, of early-transition-metal-catalyzed reactions of SCBs using earth's second abundant titanium as a catalyst. Notably, orthogonal selectivity was observed. Selective activation of the relatively inert C(sp3)-Si bond was achieved in the case of benzosilacyclobutenes, a selectivity that has rarely been achieved using other metals. Even for silacyclobutanes with C(sp3)-Si bonds only, our titanium system also shows complementary selectivity towards late transition metals to give distinct products. Thus, structurally varied SCBs and alkenes were reacted in our system to afford structurally diverse silicon-containing products that are otherwise difficult to obtain using other transition metals.

Assessment of Some Trace Elements in Workers’ Blood in Fuel Stations in Al-Nasiriyah City

Environmental pollution has become a major problem in the world, especially due to the rapid development of industries related to hydrocarbons such as fuels and polluting products. This situation is considered a serious threat to the environment and people due to its impact on human health and other living things. This study aimed to assess the trace element levels (Lead, Cadmium, Nickel, Arsenic) in the serum of workers in the fuel stations in central region of Thi-Qar Province. 60 people were selected from a group of workers in the age category (19 to 50 years), with work experience (1 to 5 years), some of whom were smokers and others were non-smokers. The study involved workers from three stations: ( Al-Raya, Al-Noor, and Thi-Qar). Control group incorporated from university students who were working remotely. The measurements were conducted at the laboratories of the Southern Technical College at Thi-Qar University. The statistical analysis revealed that the levels of the four metals (Pd >Ni > As > Cd) in individuals working at fuel stations are higher compared to the control group. In addition, the concentration of these metals in the blood of smokers is higher than that of non-smokers. The study also confirmed that all trace elements increase in the autumn season. Compared to the winter season, the concentration of trace elements in the autumn season was (20.3, 2.425, 2.068, 0.2.7) μg/dl, while their concentration in the winter was (14.4, 1.339, 1.218, 0.129) μg/dl. T

Interplay Between Metal and Acid Sites Tunes the Catalytic Selectivity Over Pd/Nanodiamond Catalysts.

Metal and acid sites are two of the most crucial catalytically active components in heterogeneous catalysis. While variations in the size, morphology, and heterogeneity of metal species, or the manipulation of the strength, location, and density of acid sites, could significantly impact the catalytic performance, the combination and interplay between these sites are even more critical and have been a recent research focus. To achieve highly efficient and selective synergistic catalysis, it is desired to design a catalyst capable of orchestrating the sequential transformation of all reactants and intermediates at different active sites. In this study, we demonstrate that both acid and metal (Pd) sites can be introduced onto a nanodiamond@graphene (NDG) support particle through simple air oxidation and metal salt deposition-precipitation methods, respectively. The presence and assembly of these two catalytically active sites significantly alter the reaction network for the cyclohexanol conversion reaction. Under this strategy, the selectivity toward designated products─cyclohexene, phenol, and benzene─can be precisely tuned by the presence and patterning of these two sites on the nanodiamond particles. Specifically, we show that the catalyst with both acid sites and Pd ensemble sites, i.e., Pd/NDG, can efficiently convert cyclohexanol through consecutive dehydration and dehydrogenation reactions to form benzene with high selectivity (>80%). These findings underscore the potential of integrating metal and acid sites to design advanced catalysts with tailored reactivity and selectivity, paving the way for more efficient and versatile catalytic processes in industrial applications.

High-performance single-atom M/TiO2 catalysts in the reverse water-gas shift reaction: A comprehensive experimental and theoretical investigation

Single-atom catalysts (SACs) offer high efficiency and selectivity in chemical reactions but face challenges in converting CO2 to CO via the reverse water gas shift (RWGS) reactions. This study addresses these challenges by anchoring three noble metals (Ir, Pd, and Ru) onto titania (TiO2) and analyzing their performance. Comprehensive characterization techniques, including electron microscopy, confirmed the uniform dispersion of metal atoms on TiO2. Among the catalysts, Ir/TiO2 exhibited the best results, achieving an 84 % CO2 conversion rate and ∼98 % CO selectivity, surpassing Pd/TiO2 and Ru/TiO2, which gained 56 % and 52 % conversion, respectively. In-situ gas transmission electron microscopy revealed the catalytic behavior of Ir/TiO2, showing Ir atom mobility and the formation of ∼1 nm nanoclusters. Density functional theory (DFT) and in-situ diffuse reflectance infrared spectroscopy (DRIFTs) further explained that the atomically dispersed Ir sites in Ir/TiO2 follow a hydrogen-assisted mechanism, with the COOH* intermediate desorbing and dissociating into CO. These findings suggest SACs' potential to facilitate greener chemical processes and reduce greenhouse gas emissions.

Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

AbstractThe development of privileged thiophene‐type ligand remains highly desirable, owing to the high coordination ability of sulfur atom to most of the soft metals. Herein, a new class of C2‐symmetric rigid chiral tertiary amine‐derived dioxide ligands with a coordinating bithiophene bridge was developed in a convenient synthetic route with 25–62% overall yields. The bithiophene‐2NO‐palladium(II) catalyst system was generated in situ and found to be highly capable catalyst in the asymmetric Friedel‐Crafts alkylation of indoles. Excellent yields (up to 92%) and high enantioselectivities (up to >99% ee) are obtained for a wide range of substrates under mild conditions. Control experiments and DFT calculations revealed the origins of the enantioselectivity. This represented the first example of chiral thiophene ligands coordinating with soft metal Pd(II) in the asymmetric Friedel‐Crafts alkylation. Experiments revealed that the counteranion is involved in the stereoselectivity‐determining step in this soft palladium(II) catalysis, and the additional NO and thiophene in ligands can act as the second chelation site and thus reduce the amount of free metal ions for suppressing background reaction in the catalytic system.

Electrodeposition of Extremely Cu-Rich CuPd Bimetallic Nanoparticles from an Amide-Type Hydrophobic Protic Ionic Liquid

Abstract Cupric oxide (CuO) and palladium(II) acetate (Pd(Ac)2) were dissolved into the amide-type hydrophobic protic ionic liquid (IL), protonated-betaine bis((trifluoromethyl)sulfonyl)amide ([Hbet][TFSA]), to produce the Cu(II) and Pd(II) species for the electrodeposition of metallic Cu, Pd, and CuPd nanoparticles (NPs). Unlike the electrodeposition conducted in common aqueous electrolytes containing the equivalent amounts of Cu and Pd ions, Cu-rich rather than Pd-rich CuPd co-deposits were obtained from the IL [Hbet][TFSA]; which might result from the retardation of Pd deposition on preferentially electrodeposited Cu surface or the formation of a new metal species when both metal ions co-existed in the IL, leading to an uncommon large overpotential needed to reduce the species into Pd metal. The surface morphologies of CuPd NPs significantly relied on their elemental compositions that could be controlled by the concentration of Pd(II) and/or the applied electrodeposition potential. CuPd NPs with different Pd contents showed very different responses in the reaction current of nitrate reduction. Nevertheless, the CuPd NPs regardless of the Pd contents showed advantages over the Cu nanoparticles in the electrochemical reduction of nitrate, which might be due to the synergistic effects between the Cu and Pd atoms.

Oxidative Coupling: An Important Tool for Pyrrole Synthesis

: In oxidative coupling, two molecules combine with the help of different oxidants and transition metals. It is used to form various natural and synthetic compounds. Oxidative coupling reactions catalyzed by transition metals (Pd or Cu), Iodine, Cobalt, Ti, etc, are used widely for the synthesis of pyrroles. Pyrrole is a 5-membered heterocyclic ring structure that consists of a single nitrogen. Several methods have been adopted and reported for the synthesis of pyrroles and their analogs in the recent past. Synthesis of pyrrole via oxidative coupling takes place in the presence of various catalysts, bases, and solvents and at different temperatures and times. In another method, Oxidative reactions between diols and primary amines utilizing copper/nitroxyl as the catalyst also yield pyrroles. Rhodium has also been used as a catalyst in oxidative coupling reactions between alkynes and carboxylic acid (substituted by heteroarene or arene) to obtain pyrroles. Paal-Knorr reaction is also one of the most common reactions in the synthesis of pyrrole. In the present study, we summarized different oxidative reactions that have been reported for the synthesis of pyrrole. Hopefully, the study will be helpful for the researchers.

Atomic behaviors in PdRu solid-solution nanoparticles on CeO2-ZrO2 support for the three-way catalytic reaction

Understanding the behavior of noble-metal catalysts is a key point of catalysis research aimed at reducing the environmental and economic costs associated with the increased use of automobiles. In this study, the atomic-behaviors of Ru and Pd atoms in PdRu solid-solution nanoparticles (NPs) supported on CeO2-ZrO2 (CZ) as a Rh-free three-way catalyst in a modeled three-way catalytic reaction (TWCR) were elucidated using a gas conversion analysis, transmission electron microscopy, and in-situ X-ray absorption fine structure spectroscopy. We found that the PdRu NPs enlarged by the annealing effect separated a smaller grain size with the Pd-rich and Ru-rich phase under TWCR. Most of the oxidation and reduction reactions under the modeled TWCR occurred on the Ru. However, the Pd metals acted as a major role of the reduction of NO gas and oxidation of CO and C3H6 gas. Ru atoms just is a minor role during the modeled TWCR. This study demonstrates the potential of PdRu NPs as a three-way catalyst and reveals the atomic-behavior and catalytic role under the modeled TWCR.

A bionic palladium metal-organic framework based on a fluorescence sensing enhancement mechanism for sensitive detection of phorate.

We have developed a biomimetic fluorescent nanoprobe (Pd-MOF) that can accurately identify phorate at a fixed wavelength for rapid, sensitive and selective detection. Pd-MOF was a nanoparticle (260.00 ± 27.83 nm) based on the linkage of Pd metal and a TCPP organic framework. It could detect phorate according to the fluorescence principles similar to that of the bioluminescence of Chrysaora pacifica (substance interaction and chromophore fluorescence enhancement). When phorate molecules enter the pores of Pd-MOF and interact with each other, the energy transfer process is stimulated, and the fluorescence signal is significantly enhanced, thereby improving the detection sensitivity. According to shift of the white line in the XANES energy spectrum and the DFT results, phorate increased the energy gap of Pd-MOF from 0.025 eV to 0.046 eV, enhanced the stability of the system, and thus achieved fluorescence enhancement. The sensitivity of Pd-MOF was due to its much smaller energy gap (<80 times) than other metal MOFs and thus it was easier to get excited. The linear detection range for the phorate of the nanoprobe in the water system was 0.01-100 ppb, and the detection limit was 0.0017 ppb. The response time of the Pd-MOF nanoprobe to phorate was 45 seconds. The detection of phorate in tap water, pear and cabbage samples showed that the recovery rates were in the range of 87.69-106.12%, and the relative standard deviation (RSD) was less than 11.16%, which verified the possibility of Pd-MOF nanoprobe in practical application. The sensitive and specific recognition of phorate by Pd-MOF nanoprobe and the development of a phorate test strip (Pd-MOF@paper) confirmed its potential application in pesticide residue detection.

A Carbon-Particle-Supported Palladium-Based Cobalt Composite Electrocatalyst for Ethanol Oxidation Reaction (EOR)

For the first time, carbon-particle-supported palladium-based cobalt composite electrocatalysts (abbreviated as PdxCoy/CPs) were prepared using a calcination–hydrothermal process–hydrothermal process (denoted as CHH). The catalysts of PdxCoy/CPs prepared using CoC2O4·2H2O, (CH3COO)2Co·4H2O, and metallic cobalt were named catalyst c1, c2, and c3, respectively. For comparison, the catalyst prepared in the absence of a Co source (denoted as Pd/CP) was identified as catalyst c0. All fabricated catalysts were thoroughly characterized by XRD, EDS, XPS, and FTIR, indicating that PdO, metallic Pd, carbon particles, and a very small amount of cobalt oxide were the main components of all produced catalysts. As demonstrated by the traditional electrochemical techniques of CV and CA, the electrocatalytic performances of PdxCoy/CP towards the ethanol oxidation reaction (EOR) were significantly superior to that of Pd/CP. In particular, c1 showed an unexpected electrocatalytic activity for EOR; for instance, in the CV test, the peak f current density of EOR on catalyst c1 was 129.3 mA cm−2, being about 10.7 times larger than that measured on Pd/CP, and in the CA test, the polarized current density of EOR recorded for c1 after 7200 s was still about 2.1 mA cm−2, which was larger than that recorded for Pd/CP (0.6 mA cm−2). In the catalyst preparation process, except for the elements of C, O, Co, and Pd, no other elements were involved, which was thought to be the main contribution of this preliminary work, being very meaningful to the further exploration of Pd-based composite EOR catalysts.

A DFT and cluster expansion study of (Fe,Ni)9S8 pentlandite and unravelling doping with Mn, Co, Cu and precious metals

This study used density functional theory (DFT) adopting the universal cluster expansion (UNCLE) technique to generate different structures for (Fe,Ni)9S8 pentlandite and doped with Mn, Co, Cu and precious metals (Ru, Rh, Pd, Os, Ir and Pt) on the Ni and Fe tetrahedral (T) sites. The cluster expansion (CE) depicted the Fe-rich Fe5Ni4S8 structure with space-group of P42/nmc (tetragonal) as the most stable. The doped Fe5Ni4S8 structure on the Fe(T) with Mn, Cu, Rh, Pd, Ir and Pt changed from tetragonal to cubic structures, while doping with Co, Ru and Os remained tetragonal. Doping on the Ni(T) with Co, the structure changed from tetragonal to cubic, while doping with Mn, Cu, Ru, Rh, Pd, Os, Ir and Pt the structure remained tetragonal. It was found that doping with Pd on the Fe(T) generated the most thermodynamically stable compound (Fe3Pd2Ni4S8) with heats of formation of −130.24 meV. The density of states (DOS) showed that the Pd and Pt were the most preferred substitution of Fe(T) in the pentlandite structure, while the Co preferred the Ni(T) sites. In addition doping with Mn on Fe(T) and Ru doped on Ni(T) induced magnetism to the structure. This study predicted various compositions of dopants on pentlandite and laid a foundation for prediction of new mineral-compounds using DFT-CE method.

Photoreduction deposition preparation of UV-light-driven Pd nanoparticles/ZnWO4 nanorods photocatalyst

UV-light-driven Pd nanoparticles/ZnWO4 nanorods photocatalyst was prepared by photoreduction deposition method. Effects of phase, morphology and photocatalytic properties on different weight contents of Pd loaded on ZnWO4 nanorods were analyzed by XRD, SEM, TEM and XPS instruments and discussed in this research. They showed that the metallic Pd nanoparticles were uniformly decorated on the high crystalline wolframite ZnWO4 nanorods. The 5% Pd/ZnWO4 nanocomposites exhibited the highest rhodamine B (RhB) degradation of 92.89% within 240 min under UV light irradiation.

Novel synthesis of reduced PdO-WO3 hybrids for enhanced photoelectrochemical water splitting

In this study, a novel synthesis approach for WO3 nanoparticles and their hybrids is proposed, followed by an investigation of their photoelectrochemical performance for water splitting applications. The surface modification of WO3 nanoparticles is carried out by immersing them in a Pd precursor solution, followed by calcination to obtain PdO-WO3 hybrid nanoparticles. Subsequently, the PdO-WO3 is reduced in a hydrogen (H2) environment to prepare PdOx-WO3-y hybrid material. XPS analysis revealed that H2 reduction converts residual metallic Pd to PdH and simultaneously generates oxygen vacancy defects in WO3 hybrid nanoparticles, as confirmed by EPR analysis. Additionally, TPR analysis further confirms the H2-induced reduction in the PdO-WO3 hybrid at a lowered temperature of 150 °C. The optical band gap energy of PdOx-WO3-y hybrid nanoparticles is slightly reduced (by 0.06 eV) compared to that of the PdO-WO3 reference sample. Photoelectrochemical measurements were conducted to assess the impact of these tailored modifications on the performance of conventional PdO-WO3 nanoparticles. The reduced PdOx-WO3-y catalyst exhibits an approximatly ∼22 % improvement in incident photon-to-current conversion efficiency (IPCE), over the unreduced PdO-WO3. The PEC efficiency improvement was attributed to the composite electronic structure changes introduced during the annealing process. Mott-Schottky measurements confirm that the reductive treatment consolidates the material’s two distinct flat band potentials (Efb) into with a single intermediate energy level and increases the charge carrier concentration. This study presents a straightforward method to generate oxygen vacancy defects in hybrid metal oxides and provides a convenient method for band gap engineering for photoelectrocatalytic applications.

Turning on Low-Temperature Catalytic Conversion of Biomass Derivatives through Teaming Pd1 and Mo1 Single-Atom Sites.

On-purpose atomic scale design of catalytic sites, specifically active and selective at low temperature for a target reaction, is a key challenge. Here, we report teamed Pd1 and Mo1 single-atom sites that exhibit high activity and selectivity for anisole hydrodeoxygenation to benzene at low temperatures, 100-150 °C, where a Pd metal nanoparticle catalyst or a MoO3 nanoparticle catalyst is individually inactive. The catalysts built from Pd1 or Mo1 single-atom sites alone are much less effective, although the catalyst with Pd1 sites shows some activity but low selectivity. Similarly, less dispersed nanoparticle catalysts are much less effective. Computational studies show that the Pd1 and Mo1 single-atom sites activate H2 and anisole, respectively, and their combination triggers the hydrodeoxygenation of anisole in this low-temperature range. The Co3O4 support is inactive for anisole hydrodeoxygenation by itself but participates in the chemistry by transferring H atoms from Pd1 to the Mo1 site. This finding opens an avenue for designing catalysts active for a target reaction channel such as conversion of biomass derivatives at a low temperature where neither metal nor oxide nanoparticles are.

Advancements in transition metal-catalyzed 1,2,3-triazole synthesis via azide–alkyne cycloaddition

Abstract 1,2,3-triazoles have emerged as important structural motifs in chemical biology, attracting increasing focus in recent years because of their wide range of uses. These compounds can be efficiently synthesized using click reactions. Its versatility makes it valuable in drug discovery and materials science. Significant advancements have been made in recent years in the process of making 1,2,3-triazoles, reflecting the growing curiosity and investment in the area of research. The catalytic performance of transition metals Cu, Ir, Rh, Ru, Ni, Pd, Au, Ag, and Zn, which were used as ligands and salts in the azide–alkyne cycloaddition method of 1,2,3-triazole synthesis, has been covered in this review. Cu-complexes and salts were found to be more effective for selective synthesis among all transition metals. Furthermore, it is determined that some azide–alkyne reactions are entirely catalytic in nature and cannot be carried out as such by switching transition metals.

Point‐of‐care testing of DNA damage markers‐8‐hydroxy‐2′‐deoxyguanosine based on cobalt‐iron‐platinum‐ruthenium/N doped ordered mesoporous carbon

AbstractIn this work, we achieved point of care detection of DNA damage marker 8‐hydroxy‐2’‐deoxyguanosine (8‐OH‐dG) on tetrapartite metal nanoparticles loaded ordered mesoporous carbon composite nanomaterials (Co‐Fex‐Pt−Pd@NOMC). Nitrogen doping and co‐metal loading were achieved using dopamine as nitrogen, carbon sources and metal linker. In addition, the presence of catechol groups in dopamine with strong affinity for metal ions, make the simultaneous confinement of metals inside and outside the pores of ordered mesoporous carbon. Then, Fe, Pt and Pd metal nanoparticles were introduced to interact with Co nanoparticles to form four‐in‐one alloy nanoparticles by oil bath and carbonisation. The finally formed Co−Fe6‐Pt−Pd@NOMC nanocomposites exhibited excellent catalytic performance for the determination of 8‐OH‐dG. A lower limit of detection (LOD) of 0.044 μM, a wide linear range (0.175 μM–118.375 μM) and strong stability, reproducibility and selectivity were obtained. In addition, Co−Fe6‐Pt−Pd@NOMC realised the detection of 8‐OH‐dG in real human urine sample. At the same time, 8‐OH‐dG after DNA damage and guanine damage were also studied in this work. The electrochemical response of 8‐OH‐dG was combined with DNA damage to verify the mechanism of DNA damage. New solutions and idea were provided for the preparation of inorganic nanocomposites for the detection of 8‐OH‐dG in this work.

DFT insights upon Pd assisted MoX2 (X = Se, S, Te) capture of air decomposition products (CO, NO2) in switch cabinet

The MoSe2, MoS2, and MoTe2 substrates are selected for testing the decomposition products of air (CO, NO2) in the switch cabinet. The metal Pd doping method is introduced to improve the detection ability of the substrate. The effect of Pd on the substrate is firstly studied, it is found that Pd can effectively improve the conductivity of the substrate by analyzing the structures, binding energy, band gap and state density changes. The adsorption of the target gases on the initial substrates is physical adsorption, and the addition of Pd enhances the adsorption capacity of the three substrates for CO and NO2 and transforms it into chemical adsorption. After the gas is adsorbed on the three modified substrates, it will cause a decrease in the band gap, and the change caused by NO2 is greater than that of CO. By analyzing the sensitivity and recovery time, it is found that the three modified substrates can effectively distinguish the two gases, and each adsorption system has a suitable recovery time at the corresponding test temperature. The results of this study can provide theoretical support for MoSe2, MoS2, and MoTe2 in detecting the decomposition products of air inside switch cabinet.

Manganese- and Iron-Catalyzed Carbonylation Reactions: A Personal Account

AbstractTransition-metal-catalyzed carbonylative transformations have been widely employed to convert CO gas into valuable carbonyl-containing molecules, mainly using noble metals (Pd, Rh, Ir, Ru) and more recently nickel and other catalysts. Although noble-metal catalysts have the advantage of reaction efficiency, their high-cost has led scientists to explore alternative procedures. Also under these backgrounds, we carried out some studies on nonexpensive metal-catalyzed carbonylative transformations. In this Account, we summarize the carbonylation reactions developed in our research group by using manganese and iron catalysis. These carbonylation reactions proceeded either via SET (single-electron transfer) or TET (two-electron transfer) mechanism.1 Introduction2 Manganese-Catalyzed Carbonylation of Alkyl Chlorides3 Manganese-Catalyzed Carbonylation of Alkyl Iodides4 Iron/Copper-Catalyzed Carbonylation of Alkyl Bromides5 Iron-Catalyzed Carbonylation of Alkyl Bromides6 Iron-Catalyzed Carbonylation of Alkyl-Boronic Pinacol7 Iron-Catalyzed Aminoalkylative Carbonylative Cyclization of Alkenes8 Conclusion and Outlook