Inorganic Chemistry Commons^™

Designing Surface-Induced Entatic States In Copper Complexes For Tunable Reactivity, Rachel Kiser

Senior Theses

Copper catalysts play an important role in electrocatalytic oxidation reactions due to their redox flexibility and relative abundance compared to noble metal catalysts. In biological systems, copper metalloenzymes often achieve enhanced reactivity through an entatic state. Entasis is described as an active site or metal center being constrained to a geometric and electronic state, minimizing primary sphere reorganization energy and achieving higher rates of electron transfer.  This study investigates whether entasis can be achieved in synthetic molecular catalysts by immobilizing Cu(I) complexes onto metal oxide surfaces. Two Cu(I) complexes bearing carboxylate-functionalized ligands were examined both in homogeneous solution and when …

Direct Partial Oxidation Of Methane To Methanol Using Dioxygen Over Superhydrophobic Modified Catalysts, Oluchukwu V. Igboenyesi

Chemistry & Biochemistry Dissertations - Archive

Various methods for enhancing catalysts activity and productivity in gas to liquid synthesis like Direct Methane to Methanol Conversion and Fischer Tropsch Synthesis have been studied over the years. Some of these methods include the use of promoters, bifunctional catalysts, introducing steam, optimizing reaction conditions and catalyst modification. The choice of catalysts and their modification plays a critical role in improving the overall productivity in gas to liquid synthesis.

This research explored the superhydrophobic modification of heterogenous catalysts used in Direct Methane to Methanol Conversion (DMTM) and Fischer Tropsch Synthesis (FTS). The catalysts were modified with Perfluoro alkyls (PFSMA). The …

Catalytic Innovation For Sustainable Styrene Production: Green Chemistry Strategies Utilizing Octahedral Ruthenium (Ii) Complexes Supported By A Single Bipyridine Ligand, Kennedy G. Musso, Brandon Quillian, Clifford Padgett, Jose Jimenez

College of Graduate Studies: Theses & Dissertations

This study investigates: 1) the synthesis and reactivity of the mono- substituted systems, [κ²-(t-bipy)Ru(NCMe)2(Ph)(PR3)][BArF'] supported by different ancillary ligands PR3 = (P(OCH3)3 and P(CH3)3) and a single bidentate ligand, 4,4′-di-tert-butyl-2,2′-bipyridine (t-bipy), and 2) UV/heat formation of di-PR3 and tri-PR3 systems supported by a single bidentate ligand to better understand the mechanism of styrene production. Utilizing [(η6-p-cymene)RuI(µ-I)]2 (1), the complexes (η6-p-cymene)RuI2(P(OCH3)3) (2) and (η6-p-cymene)RuI2(P(CH3)3) (3) were synthesized and phenylated to produce (η6-p-cymene)RuI(Ph)(PR3) (6; PR3 = P(OCH3)3 and 7; PR3 = P(CH3)3). Complex 4, (η6-p-cymene)RuCl2(P(CH3)3), was also synthesized and phenylated to produce (η6-p-cymene)RuClPh(P(CH3)3) (5) to understand the impact of chloride versus iodine …

Synthesis Of Chemical Fuels And Feedstocks From Co2 For Extraterrestrial Applications, Samuel Keith Conlin

Graduate Theses and Dissertations

The reduction of CO₂ into products for either the storage of renewable electricity or to act as a source of renewable feedstock for industry, is not economically feasible given the current costs of renewable energy. Significant amounts of work have gone into attempting to optimize both electrochemical and nonthermal plasma-based CO₂ reduction systems in an attempt to reduce side reactions and improve energy efficiency in order to meet cost feasibility targets. These techniques can also be adapted for In-Situ Resource Utilization (ISRU) contexts, which are far less sensitive to the cost of renewable energy yet have more strenuous …

Molecular And Hybrid Catalysts For Selective Hydrodeoxygenation Of Lignin Model Compounds, Jacob G. Tillou

Theses and Dissertations

Lignin is a highly aromatic, branched polymer and could be utilized as a renewable source of liquid fuel. The advent of “lignin-first” depolymerization processes have allowed for the high-yield isolation of oxygenated aromatic monomers from lignin. These oxygenated aromatic compounds are lower in energy and stability than their deoxygenated counterparts. Selective deoxygenation of these compounds would result in stable, higher value liquid fuels. Using molecular catalysts, selective deoxygenation, or hydrodeoxygenation (HDO), of lignin-derived compounds in the presence of hydrogen is possible.

Immobilization of these molecular catalysts on metal oxide surfaces eliminates the possibility of bimolecular decomposition and allows for easier …

Proton-Coupled Electron Transfer To Drive Biomass Conversion, Cody Canote

Graduate Theses and Dissertations

Meeting rising demands for commodity chemicals while simultaneously easing reliance on fossil fuels presents one of the most substantial challenges for chemistry to date. Biomass has emerged as a sustainable precursor to commodity chemicals but requires substantial deoxygenation to displace petrochemicals. Development of efficient catalysts to achieve these transformations remains one of the central goals of inorganic and organometallic chemistry. Electrochemical strategies to propel biomass conversion are attractive, providing the driving force for reactivity and insights into catalyst mechanism. This work focuses on proton-coupled electron transfer (PCET) to facilitate redox catalysis in biomass up conversion and homolytic bond cleavage in …

Modulating Covalency In A Ni-H-Al Subunit: Synthesis And Characterization Of A Series Of Electronically Differentiating Ni-Al Heterometallics, Aleida Guadalupe Gonzalez

Theses and Dissertations

Metal hydrides are moieties that are present in a variety of applications as intermediates in catalysis. Despite the vast utilization of metal hydrides, monometallic metal hydride complexes bear limitations in inert-bond activation and functionalization. A strategy to overcome these limitations and access more challenging reactivity is utilizing metal-metal cooperativity on a single platform to further activate hydride moieties. Although incorporating multiple metal centers on a single ligand scaffold has been realized, access to heterometallic hydride-bearing complexes is a greater synthetic challenge. Given the limitations in accessing such systems, the reactivity and electronic structure of heterometallic hydrides are seldom studied. Recently, …

Computational Investigation Of Transition Metal Photoredox Catalysis: Redox Property Tuning Via Ligand Modification, Christian Fernando Sandoval Pauker

Open Access Theses & Dissertations

In the last decade, photoredox catalysis has become a powerful tool in synthetic chemistry. It relies on the ability of catalytic systems that facilitate energy-demanding redox reactions thanks to photoinduced electron transfer processes. This dissertation focuses on the computational investigation of the redox properties of transition metal photoredox catalysts using density functional theory (DFT) calculations. The research systematically explores the effects of altering redox-active ligands on the thermodynamics of electron transfer events in the photoredox cycle. The electronic structure changes throughout oxidative and reductive quenching cycles are analyzed, with a particular focus on Cu(I) complexes. Through computational techniques, insights into …

Mechanistic Investigation Of C—C Bond Activation Of Phosphaalkynes With Pt(0) Complexes, Roberto M. Escobar, Abdurrahman C. Ateşin, Christian Müller, William D. Jones, Tülay Ateşin

Research Symposium

Carbon–carbon (C–C) bond activation has gained increased attention as a direct method for the synthesis of pharmaceuticals. Due to the thermodynamic stability and kinetic inaccessibility of the C–C bonds, however, activation of C–C bonds by homogeneous transition-metal catalysts under mild homogeneous conditions is still a challenge. Most of the systems in which the activation occurs either have aromatization or relief of ring strain as the primary driving force. The activation of unstrained C–C bonds of phosphaalkynes does not have this advantage. This study employs Density Functional Theory (DFT) calculations to elucidate Pt(0)-mediated C–CP bond activation mechanisms in phosphaalkynes. Investigating the …

Publication Of Undergraduate Experiments, Development Of Additional X-Ray Crystallography Experiments, And Proof-Of-Concept Cyclopropanation Reactions, Alain Beauparlant

Electronic Theses and Dissertations

Single crystal X-ray crystallography instructional materials were developed using a variety of compounds including sugar, Epsom salt, pyrite, copper(II) acetate, and rhodium(II) acetate. Rhodium(II) acetate was reacted with a variety of functionalized benzonitriles, and when crystals were obtained, characterized using single crystal X-ray crystallography. Rhodium(II) acetate with adducts of 4-nitrobenzonitrile and 4-(dimethylamino)benzonitrile were also characterized using proton NMR spectroscopy and Fourier Transform Infrared Spectroscopy. Rhodium(II) acetate with adducts of 4-(dimethylamino)benzonitrile was used as a catalyst in a proof-ofconcept reaction to determine if it acts as a catalyst in cyclopropanation reactions. Further, the new rhodium(II) acetate dinitrile compounds were investigated to …

Improved Stoichiometric Synthesis Of Ccc-Nhc Pincer Rh Complexes And Catalytic Activity Towards Dehydrogenative Silylation And Hydrosilylation Of Alkenes, Enock Amoateng

Theses and Dissertations

N-Heterocyclic carbenes (NHCs) have attracted growing interest not only as successful ancillary ligands in a wide variety of transition-metal-catalyzed reactions but have also shown to offer photophysical and electrochemical properties. The metalation/transmetalation strategy using [Zr(NMe₂)₄] as initial metalating reagent offers an efficient approach to the preparation of CCC-NHC pincer complexes of the late transition metals such as Rh and Ir. In the process of investigating an intermediate and the mechanism of the metalation/transmetalation to Rh sequence, a mixed valent bimetallic CCC-NHC pincer Rh complex with two chloro ligands bridged between a [(CCC-NHC)Rh(III)] and a [Rh(I)(COD)] fragment …

Ambient Ammonia Synthesis Via Microwave-Catalytic Materials And Plasma Chemistry, Siobhan Brown

Graduate Theses, Dissertations, and Problem Reports (ETD)

Ammonia is critical to supporting human life on earth because of its use as fertilizer. The Haber-Bosch process to produce ammonia has been practiced for over 100 years. This process operates at high pressure and temperature to overcome the thermodynamic and kinetic limitations of the ammonia synthesis reaction thus researchers have tried to overcome it for decades. At present this process represents 1% of global energy usage and 2.5% of global CO₂ emissions. The proposed chemical looping ammonia synthesis approach seeks to reduce the environmental impact of this critical process and to elucidate microwave-catalytic principles.

This research aims to …

Calcium Bistriflimide-Mediated Sulfur (Vi)–Fluoride Exchange (Sufex): Mechanistic Insights Toward Instigating Catalysis, Nicholas Ball, Brian Han, Samuel R. Khasnavis, Matthew Nwerem, Michael Bertagna, O Maduka Ogba

Pomona Faculty Publications and Research

We report a mechanistic investigation of calcium bistriflimide-mediated sulfur(VI)–fluoride exchange (SuFEx) between sulfonyl fluorides and amines. We determine the likely pre-activation resting state─a calcium bistriflimide complex with ligated amines─thus allowing for corroborated calculation of the SuFEx activation barrier at ∼21 kcal/mol, compared to 21.5 ± 0.14 kcal/mol derived via kinetics experiments. Transition state analysis revealed: (1) a two-point calcium-substrate contact that activates the sulfur(VI) center and stabilizes the leaving fluoride and (2) a 1,4-diazabicyclo[2.2.2]octane additive that provides Brønsted-base activation of the nucleophilic amine. Stable Ca–F complexes upon sulfonamide formation are likely contributors to inhibited catalytic turnover, and a proof-of-principle redesign …

C-H On The Oxo Ferryl Wheel: Comparison Of Pyridine And Imidazole-Substituted Ligands For C-H Activation And Functionalization, Elizabeth Milem

Electronic Theses and Dissertations

The selective and efficient transformation of hydrocarbon feedstocks is of high value for industry and research. While Shilov-type organometallic methods have facilitated this goal, systems designed after nature’s use of cheap and abundant iron-based enzymes are desired for wider-scale applications. This work establishes hydrocarbon oxidation efficiency of synthetic pyridine-based ligands (BPMEN, BPMPN) compared to commercially available TPA with in situ generated catalysts. Literature studies of traditionally synthesized BPMEN systems and initial in situ studies offered evidence for enhanced reactivity (TON) as compared to TPA. Expansion to a propyl backbone to produce BPMPN tested the increased chelate ring size’s impact on …

A Comparative Study Of Two Nickel-Based Suzuki-Miyaura Hybrid Molecular Catalysts, Mollie Morrow

Senior Theses

Two molecular nickel-based catalysts, (2,2’bipyridine-4,4’-carboxylic acid)nickel(II) chloride and (2,2'-bipyridine-4,4'-diamidopropylsilatrane)nickel(II) chloride, were synthesized and subsequently attached to a solid support in the form of amorphous silicon dioxide to create two hybrid molecular/heterogeneous catalysts. Characterization using ICP-MS and ATR-FTIR confirms that both catalysts are bonded to the SiO₂ support. The catalysts were both able to catalyze a Suzuki-Miyarua cross-coupling which their molecular counterparts were unable to; the carboxylate catalyst was able to achieve yields of 10% and the silatrane catalyst achieved yields of up to 50%. Post-reaction analysis indicated that while some catalyst desorption occurred in both complexes, active catalytic species …

Cobalt, Molybdenum, And Nickel Complexes, Natural Zeolites, Epoxidation, And Free Radical Reactions, Nicholas K. Newberry

Dissertations, Master's Theses and Master's Reports

Chapter 2 is based on the synthesis and study of the compounds of the bidentate ligand ((5-phenyl-1H-pyrazol-3-yl)methyl)phosphine oxide with molybdenum and cobalt as the transition metal. The complexes were analyzed via FTIR, NMR, UV-Vis, Fluorescence Spectroscopy, TGA, DFT, and XRD. Chapter 3 resulted in the synthesis of the complexes [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6) of which [Ni(II)SRSRL](Cl)(PF6) had not been previously analyzed. Both products were analyzed via FTIR, NMR, UV-Vis, CV, DFT, and XRD. Chapter 5 contains the results of the characterization and modification of 4 natural zeolites (AZLB-Na, AZLB-Ca, NM-CA, NV-Na) from the United States in an attempt to increase the …

Synthesis And Characterization Of Redox Non-Innocent Ligand Supported Transition Metal Complexes, Adriana Marie Lugosan

Dissertations

Catalysis is an integral part of society, which is often taken for granted. Over the past few years, there has been an increased effort to develop catalysts that are more environmentally friendly, selective, and energy efficient. This work focuses on the development of novel complexes made from a carefully designed non-innocent ligand together with earth-abundant and cost-effective transition metals that can be used to understand fundamental inorganic chemistry principles and serve as model systems. The work reported within validates the utility of this novel class of redox non-innocent ligand to form metal complexes with interesting properties, such as a non-porphyrin …

The Utilization Of Metal-Ligand Cooperativity For Electrocatalytic Reduction And Catalytic Hydration., Steven Cronin

Electronic Theses and Dissertations

Small molecules are building blocks for developing larger materials. These small molecules could be extremely small, such as hydrogen, or larger such as a nitrile, but their impact on the global economy is massive. This dissertation describes a catalyst for three reactions involving small molecules; 1) the hydrogen evolution reaction, 2) the carbon dioxide reduction reaction, 3) nitrile hydration. The catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) use “metal-ligand cooperativity” between the Lewis acid Zn(II) metal ion and an uncoordinated Lewis base nitrogen in the ligand framework to activate substrates. The complex has been analyzed via NMR, UV/Vis, single crystal X-ray crystallography, …

Reactions Of First-Row Transition Metal Complexes In Bis(Alkoxide) Ligand Environments With Diazoalkanes: Formation Of Carbenes Versus Reductive Coupling To Form Bridging Tetrazenes, Amanda Grass

Wayne State University Dissertations

This dissertation focuses on the design and reactions of novel late transition metal carbene complexes featuring alkoxide ligand environments. The high-valent cobalt carbene Co(OR)2(=CPh2) (OR = OCtBu2Ph), featuring short Co=C bond of 1.773(3) Å, was previously reported from the reaction of Co(OR)2(THF)2 with diphenyldiazoalkane. Magnetic and spectroscopic (EPR) studies demonstrated Co(OR)2(=CPh2) to be a low-spin S = ½ complex. Computational studies, in agreement with experimental data, suggested that the electronic structure of Co(OR)2(=CPh2) lies between intermediate spin Co(III) anti-ferromagnetically coupled to a carbene radical and a Co(IV) alkylidene. This dissertation began with investigation of this complex in carbene transfer reactivity. …

Greening Of Catalytic Processes Using First-Row Transition Metals For Atom Transfer Radical Addition And Transfer Hydrogenation, Gabrielle Pros

Electronic Theses and Dissertations

This work focused on “greening” catalytic processes, atom transfer radical addition (ATRA), which adds an alkyl halide across and alkene, and transfer hydrogenation/dehydrogenation, which reduces a carbonyl without needing direct H₂ gas. Part of “greening” of these processes is through using abundant first row metals, Cu and Ni for catalysis. One aim was to design new ligands which would be more active in these systems; the second was investigation of additives for catalyst regeneration to reduce the catalyst loading necessary for high yields.

The TPMA^* family was investigated in ATRA. Rate constants followed the expected trend, which increased …

Synthesis And Characterization Of A Homogeneous Cobalt Catalyst For The Hydrogenation Of Acetone To Isopropanol, Joselyn G. Molina

Honors Projects

To lessen environmentalstrain and decrease dependency on noble metals for catalysis, first-row metals are continuously being explored as alternative catalysts for reactions of interest, particularly those that close the carbon cycle or promote fuel production. Recently, homogeneous cobalt catalysts have been shown to be viable options for effective hydrogenation of C-O double bonds, with cobalt-triphos being of particular interest. Here, we report the characterization of synthesized a cobalt-triphos complex by nuclear magnetic resonance spectroscopy and optical spectroscopy. Analysis of the electrochemistry of the cobalt-triphos complex suggests promising electrocatalytic capability for the hydrogenation of acetone to produce isopropanol.

Preparation Of Enantioenriched Alkyltin Species And Their Application In Stereospecific Transformations, Glenn O. Ralph

Dissertations, Theses, and Capstone Projects

Organometallic reagents containing the tin-carbon bond are used extensively in modern synthetic chemistry for the formation of new bonds to carbon. Over recent decades, transition metal catalyzed cross coupling reactions between two C(sp²) centers have been widely developed. However, the introduction of a C(sp³) center complicates the catalytic cycle, and opens unproductive chemical pathways which lead to isomerization, elimination, and racemization. Our lab has developed a modified-Stille reaction to combat the deleterious effects of β-hydride elimination. Our protocol enables unactivated 2° alkyl organotin nucleophiles to undergo efficient cross coupling reactions with C(sp²) electrophiles, avoiding …

Examining The Effects Of Amino And Thiolate Ligands On The Reactivity And Selectivity Of Palladium On Carbon In Hydrogenation Reactions, Eric Liu, Christina Li

The Summer Undergraduate Research Fellowship (SURF) Symposium

Heterogeneous catalysts are used widely by chemical and energy industries because they show high reactivity but often suffer from lack of selectivity. On the other hand, ligands are commonly used in homogeneous catalysts to control the reactivity and selectivity; however, the effects of the ligands on the steric and electronic properties of heterogeneous catalysts are less understood. We examine the effects of four different ligands: 1-adamantanethiol, 1-adamantylamine, 1-dodecanethiol, and 1-dodecylamine, for the commercial hydrogenation catalyst palladium on carbon. Hydrogenation reactions are used as a screening tool to see the behavior that the different catalysts exhibit in the presence of unsaturated …

Imidazolium Ionic Liquids As Multifunctional Solvents, Ligands, And Reducing Agents For Noble Metal Deposition Onto Well-Defined Heterostructures And The Effect Of Synthetic History On Catalytic Performance, Michael Drake Ballentine

Masters Theses & Specialist Projects

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]Tf2N) was investigated as a multifunctional solvent, ligand, and reducing agent for platinum deposition onto well-defined CdSe@CdS nanorods. Platinum deposition was carried out thermally and photochemically using Pt(acac)2 as the metal precursor. Thermal deposition was investigated in [BMIM]Tf2N with and without addition of a sacrificial reducing agent, and product topology was compared with the products obtained from polyol reduction using 1,2-hexadecanediol, oleic acid, and oleylamine in diphenyl ether. Photochemically induced platinum deposition was carried out at room temperature in [BMIM]Tf2N, and product topology was compared with the photodeposition products obtained from a toluene dispersion. Thermal deposition of platinum …

Bimetallic Complexes: The Fundamental Aspects Of Metal-Metal Interactions, Ligand Sterics And Application, Michael Bernard Pastor

University of the Pacific Theses and Dissertations

Metal containing complexes have been used to catalyze various organic transformations for the past few decades. The success of several mononuclear catalysts led to transition metal catalysts used in pharmaceuticals, environmental, and industrial processes. While mononuclear complexes have been used extensively, bimetallic systems have received far less attention. Bimetallic or polynuclear sites are commonly found in metalloenzymes that perform elegant transformation in biological systems, underlying their significance. Inorganic chemists take inspiration from nature and design model bimetallic complexes to further study this cooperativity effect. A bimetallic platform offers many structural and functional differences such as the identity of the metal …

The Investigation Of Oxidative Addition Reactions Of Metal Complexes In Cross-Coupling Catalytic Cycles Based On A Unique Methodology Of Coupled Ion/Ion-Ion/Molecule Reactions, Mariah L. Parker

Theses and Dissertations

Popular catalytic cycles, such as the Heck, Suzuki, and Negishi, utilize metal centers that oscillate between two oxidation states (II/0) during the three main steps of catalysis: reductive elimination, oxidative addition, and transmetallation. There has been a push to use less toxic, cheaper metal centers in catalytic cycles, leading to interest in first-row transition metals, such as nickel and cobalt. With these metals, the cycles can potentially pass through the +1 oxidation state, which acts as reactive intermediates, undergoing oxidative additions to form products, potentially with radical characteristics. The oxidative addition steps of catalytic cycles are critical to determining overall …

Ruthenium Catalyzed Deaminative Coupling Reaction Of Amines Via C-N Bond Activation, Pandula T. Kirinde Arachchige

Master's Theses (2009 -)

C–N bond activation via transition-metal catalyst has attracted much attention during the past two decades. This strategy has become one of the most promising way to generate secondary amines, which are very important in a broad spectrum of applications in pharmaceutical industry, synthetic organic chemistry and material science. The secondary amines can be utilized as an important synthetic intermediate for further manipulations. The in-situ formed catalytic system generated from the tetranuclear Ru–H complex with 4-(1,1-dimethylethyl)-1,2-benzenediol ligand was found to be effective for the synthesis of secondary amines from the direct deaminative coupling of amines. The ruthenium catalyst was highly effective …

Homogeneous Ligand-Centered Hydrogen Evolution And Hydrogen Oxidation : Exploiting Redox Non-Innocence To Drive Catalysis., Andrew Z. Haddad

Electronic Theses and Dissertations

Hydrogen is a promising carbon-free fuel / energy carrier and is an essential building block for many industrial and agricultural processes. Rising energy demands have ignited interest in the development of carbon-free and carbon neutral energy sources. In this context, hydrogen is an attractive candidate—being energy-dense, carbon-free—and easily accessible through a two-electron reduction of water. Accordingly, many electrochemical homogeneous catalyst systems have been studied, with a focus on understanding the mechanism of hydrogen evolution proceeding through metal-hydride intermediates. However, there has been a renaissance in hydrogen evolution reaction (HER) catalyst design, with many groups implicating ligand redox non-innocence as a …

An Electrochemical Characterization Of A Vanadium-Based Deoxydehydration Catalyst, Joel Eric Baker

Graduate Theses and Dissertations

Alternative methods for the conversion of polyols into olefins, be it for carbon storage or hydrocarbon fuel production, have become prevalent in today’s chemical industry. One process in particular, deoxydehydration (DODH) has been proven effective in taking sustainable biomass derivatives and converting them through the utilization of various homogenous metal catalysts. While this process may show productive yields and material conversion, it is hindered by the need of a sacrificial reductant. This makes a novel process economically unviable and relatively unused outside of scientific research. That fact begs the question: Can the process be improved? It is proposed here that …

Ruthenium-Catalyzed Dehydrogenative And Dehydrative C-H Coupling Reactions Of Arenes With Alcohols And Carbonyl Compounds, Hanbin Lee

Dissertations (1934 -)

Despite their outstanding achievements, the requirement of preformed functional groups and wasteful byproduct formation are inherent disadvantages associated with the transition metal catalyzed cross-coupling methods. Inspired by the needs for green and sustainable chemistry, transition metal catalyzed dehydrogenative and dehydrative coupling methods have been recognized as environmentally sustainable and atom economical synthetic routes for the new C-C bond formation. The catalytic activation of C-H and C-O bonds allows the formation of coupling products from ubiquitous hydrocarbon substrates by releasing hydrogen or water byproduct. However, these novel protocols require relatively harsh conditions due to their low reactivity of C-H and C-O …