Baeyer-Villiger oxidation of 1,9-dibromopentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (1,9-dibromo-PCU-8,11-dione) was performed by using an excess amount of m-chloroperbenzoic acid (3 equivalents) and resulted in the formation of the corresponding monolactone. The reaction would not proceed to the dilactone stage. The structure of the reaction product was established unequivocally via single crystal X-ray diffraction. Baeyer-Villiger oxidation of 1,9-dibromo-PCU-8,11-dione using ceric ammonium nitrate (CAN) was also performed and afforded a mixture of lactones. Only one of these lactones, which also contained an alkene functionality, could be isolated and characterized. 1,7-dibromo-PCU-8,11-dione was also reacted with CAN, yielding the mono-lactone, which has also been characterized.

An extremely facile and novel method called spontaneous deposition, to deposit noble metal nanoparticles on a most stable form of carbon (C) i.e. diamond is presented. Nanometer sized particles of such metals as platinum (Pt), palladium (Pd), gold (Au), copper (Cu) and silver (Ag) could be deposited on boron-doped (B-doped) polycrystalline diamond films grown on silicon (Si) substrates, by simply immersing the diamond/Si sample in hydrofluoric acid (HF) solution containing ions of the corresponding metal. The electrons for the reduction of metal ions came from the Si back substrate. The diamond/Si interfacial ohmic contact was of paramount importance to the observation of the spontaneous deposition process. The metal/diamond (M/C) surfaces were investigated using Raman spectroscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffractometry (XRD). The morphology (i.e. size and distribution) of metal nanoparticles deposits could be controlled by adjusting the metal ion concentration, HF concentration and deposition time. XRD data indicate the presence of textured and strained crystal lattices of Pd for different Pd/C morphologies, which seem to influence the electrocatalytic oxidation of formaldehyde (HCHO). The sensitivity of electrocatalytic reactions to surface crystal structure implies that M/C could be fabricated for specific electrocatalytic applications. The research also …

With the reliability requirements of automobile microelectronics pushing towards near 0 ppb levels of failure control, halide induced corrosion issues in wire bonded devices have to be tightly controlled to achieve such a high reliability goal. With real-time corrosion monitoring, for the first time we demonstrated that the explosive H2 evolution coupled with the oxygen reduction reaction, occurring at the critical Al/Cu interfaces, is the key driving force for the observed aggressive corrosion. Several types of passivation coating on Cu wire surfaces to effectively block the cathodic H2 evolution were explored with an aim to disrupt this explosive corrosion cycle. The properties of the protective coating were evaluated using various analytical techniques. The surface coating exhibited high thermal stability up to 260 °C (evaluated using TGA analysis). A uniform, highly hydrophobic coating (surface contact angle of >130° with water), was achieved by carefully controlling CVD parameters such as time of deposition, surface control of Cu metal, amount of inhibitor compound loading, temperature of coating process etc. FTIR spectroscopy combined with corrosion screening was used to optimize the CVD passivated coating with strong chemisorption. SEM and EDX, XPS were carried out on various coated surfaces to understand the composition and selectivity …

Part I. The syntheses of a series of stable ferrocenylsilane compounds and their corresponding polyradical cations are reported. Electron spin properties of these molecules were investigated by cyclic voltammetry, ESR, and magnetic susceptibility measurements. All the compounds presented, showed significant electronic communication (>100 mV) between the redox centers by CV. Part II. Baeyer-Villiger oxidation of (1,9-dimethyl-PCU-8,11-dione) was performed using m-chloroperoxybenzoic acid in 1:2 molar ratios. The product obtained was the corresponding dilactone 113. The structure of the reaction products was established unequivocally via single crystal X-ray diffraction methods. The reaction of the 1,9-dimethyl-PCU-8,11-dione with 1:1 molar ratio of m-chloroperoxybenzoic acid produced again the dilactone 113, and not the expected monolactone 114. Ceric ammonium nitrate (CAN) promoted oxidation reaction of 1,9-dimethyl-PCU-8,11-dione afforded a mixture of dimethylated lactones, which indicated unique reaction mechanism pathways. These individual isomers, 115 and 116, have been isolated from these mixtures via column chromatography by using silica gel as adsorbent followed by fractional recrystallization of individual chromatography fractions. Structures of these pure products have been established unequivocally by application of single crystal X-ray crystallographic methods.

This dissertation focuses on the development, characterization, and analysis of luminescent materials and coatings for sensing applications, including CO2, heavy metals, and silver. Chapter 2 involves the use of a gold(I) pyrazolate trimer that is able to detect silver ions with an AgNP medium. Detection of silver is vital, because there is an influx of silver into our environment caused by the increased use of AgNP. Therefore, having a sensor that is able to differentiate between and detect only Ag ions is an important first step to solving the toxicity mystery of AgNPs. Chapter 3 focuses on the development of sensor coatings containing a Eu(III) based luminescent system for sensing dissolved CO2 without the aid of an absorption-based dye. It is well-known that monitoring CO2 levels in our environment is important since even at low concentrations it can cause adverse health effects to the human body. This work demonstrates a pH-sensitive Eu complex being used directly as a CO2 sensor without the aid of any other absorption-based dye. Chapter 4 explores the idea of developing a heavy metal sensor for lead and its ability to detect lead in wide concentration range upon changing the pH of the medium and the …

A brief introduction to the current state of research in the Origins of Life field is given in Part I of this work. Part II covers original research performed by the author and co-workers. Layered Double Hydroxide (LDH) systems are anion-exchanging clays that have the general formula M(II)xM(III)(OH)(2x+2)Y, where M(II) and M(III) are any divalent and trivalent metals, respectively. Y can be nearly any anion, although modern naturally occuring LDH systems incorporate carbonate (CO32-), chloride (Cl-), or sulfate (SO42-) anions. Intercalated cobalticyanide anion shows a small yet observable deviation from local Oh symmetry causing small differences between its oriented and non-oriented infrared spectra. Nitroprusside is shown to intercalate into 2:1 Mg:Al LDH with decomposition to form intercalated ferrocyanide and nitrosyl groups of an unidentified nature. The [Ru(CN)6]4- anion is shown to intercalate into layered double hydroxides in the same manner as other hexacyano anions, such as ferrocyanide and cobalticyanide, with its three-fold rotational axis perpendicular to the hydroxide sheets. The square-planar tetracyano-nickelate(II), -palladate(II), and platinate(II) anions were intercalated into both 2:1 and 3:1 Mg:Al layered double hydroxides (LDH). The basal spacings in the 2:1 hosts are approximately 11 Å, indicating that the anions are inclined approximately 75 degrees relative to …

One of the main goals of computational methods is to identify reasonable geometries for target materials. Organometallic complexes have been investigated in this dissertation research, entailing a significant challenge based on transition metal diversity and the associated complexity of the ligands. A large variety of theoretical methods have been employed to determine ground state geometries of organometallic species. An impressive number of transition metals entailing diverse isomers (e.g., geometric, spin, structural and coordination), different coordination numbers, oxidation states and various numbers of electrons in d orbitals have been studied. Moreover, ligands that are single, double or triple bonded to the transition metal, exhibiting diverse electronic and steric effects, have been investigated. In this research, a novel de novo scheme for structural prediction of transition metal complexes was developed, tested and shown to be successful.

Treatment of dichloromaleic anhydride and 1,8-diaminonaphthalene in either benzene or toluene under refluxing conditions gives low yields of the new heterocyclic compound 8,9-dichloropyrrolo[1,2-a]perimidin-10-one. This product has been isolated and characterized in solution by NMR, IR, and UV/vis spectroscopies, and the solid-state structure of 8,9-dichloropyrrolo[1,2-a]perimidin-10-one has been established by X-ray crystallography. The nature of the HOMO and LUMO levels of 8,9-dichloropyrrolo[1,2-a]perimidin-10-one has been studied by extended Hückel molecular orbital calculations.

Glutathione syntethase (GS) is an enzyme that belongs to the ATP-grasp superfamily and catalyzes the second step in the biosynthesis of glutathione. GS has been purified and sequenced from a variety of biological sources; still, its exact mechanism is not fully understood. Four highly conserved residues were identified in the binding site of human GS. Additionally, the G-loop residues that close the active site during catalysis were found to be conserved. Since these residues are important for catalysis, their function was studied computationally by site-directed mutagenesis. Starting from the reported crystal structure of human GS, different conformations for the wild type and mutants were obtained using molecular dynamics technique. The key interactions between residues and ligands were detected and found to be essential for enzyme activity.

The second order rate constants for nucleophilic substitution by methoxide of (Z)- and (E)-O-methylbenzohydroximoyl fluorides [C6H4C(F)=NOCH3] with various substituents on the phenyl ring [p-OCH3 (1h, 2h), p-CH3 (1g, 2g), p-Cl (1f, 2f), p-H (1e, 2e), (3,5)-bis-CF3 (1i, 2i)] in 90:10 DMSO:MeOH have been measured. A Hammett plot of these rate constants vs σ values gave positive ρ values of 2.95 (Z isomer) and 3.29 (E isomer). Comparison of these rates with methoxide substitution rates for Omethylbenzohydroximoyl bromide [C6H4C(Br)=NOCH3] and Omethylbenzohydroximoyl chloride [C6H4C(Cl)=NOCH3] reveal an element effect for the Z isomers of Br:Cl:F(1e) = 2.21:1.00:79.7 and for the E isomers of Cl:F(2e) = 1.00:18.3. With the p-OCH3-imidoyl halides the following element effects are found: Br:Cl:F(1h) = 2.78:1.00:73.1 for the Z isomer and Br:Cl:F(2h) = 1.97:1.00:12.1 for the E isomer. Measurement of activation parameters revealed ∆S≠ = -17 eu for 1e and ∆S≠ = -9.9 eu for 2e. Ab initio calculations (HF/6-31+G*, MP2/6-31+G*//HF/6-31+G*, B3LYP/6- 31+G*//HF/6-31+G*, HF-SCIPCM/6-31+G*//HF/6-31+G*) were performed to define the reaction surface. These calculations demonstrate a relatively large barrier for nucleophilic attack in relation to halogen loss and support the experimental findings that this reaction proceeds by an addition-elimination mechanism (AN# + DN). The imidoyl fluorides have been used to synthesize …

This dissertation focuses on the computational investigation of gold(I) acyclic diaminocarbene (ADC) complexes and their application in homogeneous gold(I) catalysis. Chapter 2 is an in-depth computational investigation of the σ- and π-bonding interactions that make up the gold-carbene bond. Due to the inherent conformation flexibility of ADC ligands, distortions of the carbene plane can arise that disrupt orbital overlap between the lone pairs on the adjacent nitrogen atoms and the empty p-orbital of the carbene. This study investigated the affect these distortions have on the strength of the σ- and π-bonding interactions. This investigation demonstrated that while these distortions can affect the σ- and π-bonding interactions, the ADC ligand have to become highly distorted before any significant change in energy of either the σ- or π-bonding interactions occurs. Chapter 3 is a collaborative investigation between experimental and computational methods, DFT calculations were employed to support the experimental catalytic results and determine the role that steric effects have in controlling the regioselectivity of a long-standing electronically controlled gold(I)-catalyzed tandem 1,6-enyne cyclization/hydroarylation reaction with indole. This study demonstrated that by sterically hindering nucleophilic attack of indole at the favored position, nucleophilic attack would occur at a secondary position leading to the selective …

The preparation of layered double hydroxides via co-precipitation of a divalent/trivalent metal solution against a base results in 1 mm LDH particles with a disorganized metal lattice. Research was performed to address these morphological issues using techniques such as Ostwald ripening and precipitation via aluminate. Another interesting issue in layered double hydroxide materials is the uptake and orientation of anions into the interlayer. Questions about iron cyanide interlayer anions have been posed. Fourier transform infared spectroscopy and powder x-ray diffraction have been used to investigate these topics. It was found that factors such as orientation, anion charge, and anion structure depended on the divalent/trivalent metal ratio of the hydroxide layer and reactivity time. The cyanide self-addition reaction is an important reaction of classical prebiotic chemistry. This reaction has been shown to give rise to amino acids, purines and pyrimidines. At cyanide concentrations similar to that expected on the early earth, hydrolysis to formamide rather than self-addition occurs. One theory to alleviate this side reaction is the use of minerals or clays that are thought to concentrate and catalyze prebiotics of interest. Layered double hydroxides have been studied as a catalyst for this reaction.

Novel cage-functionalized azacrown ethers, i.e. 51, 52, 53, 55, 57, 61 and 62, which have various crown cavity and different number of nitrogen atoms incorporated, have been prepared. X-ray structures of 53, 55 and 57 have been obtained for the study of the crown topological structure. The complexation properties of crown 51, 52, 57, 61 and 62 have been evaluated via alkali metal picrate extraction, silver picrate extraction and ESI-MS study. The novel cage-fuctionalized azacrown ethers generally exhibit high avidity and selectivity towards Ag+ versus alkali metal ions and some transition metals i.e. Cu2+, Mn2+, Zn2+, Ni2+ and Pb2+. Crown 61 displays significant avidity and selectivity toward K+ in alkali metal picrate extraction experiments vis-à-vis the remaining alkali metal picrates. Three types of ditopic ion-exchange receptors for sodium hydroxide extraction study have been designed. All of the crown ether molecules have proper cavity for selective sodium complexation and have weakly acidic ionizable alcohols for sodium-proton exchange under strongly basic conditions. Crown 80 and 81 were synthesized; key intermediates for the synthesis of crown 82, 83 and 84 have been prepared. The preparation of 99 afforded an unexpected crown 103. The preparation of 109 had been attempted, but could not be …

Three cage-functionalized polyoxacrown ethers (9, 10 and 12) and four novel cage-functionalized polyoxamonoazacrown ethers (18, 20, 25 and 29) that contain 3,5-disubstituted-4-oxahexacyclo[5.4.0.02,6.03,10.05,9.08,11]dodecane ("oxahexacyclic") moiety have been synthesized and their respective alkali metal picrate extraction profiles along with that of three analogues 13, 14 and 21 have been obtained. The observed avidities and selectivities of the host molecules toward complexation and transport of alkali metal picrates can be related to the size and shape of their respective macrocyclic cavity and the number of donor atoms. The effect of N-alkyl substitution on the complexation properties of azacrown ethers has been studied. The avidity of N-Et azacrown ethers toward complexation with alkali metal cations is generally higher than that of the corresponding non-N-alkylated hosts. However, the presence of an N-Et group appears to have a negligible effect upon their relative selectivities in their regards. The effect of pH on extraction process was studied; it was thereby determined that the alkali metal picrate extraction experiments are best performed at high pH (ca. 11-12).

Computational methods were employed to investigate catalytic processes. First, DFT calculations predicted the important geometry metrics of a copper–nitrene complex. MCSCF calculations supported the open-shell singlet state as the ground state of a monomeric copper nitrene, which was consistent with the diamagnetic character deduced from experimental observations. The calculations predicted an elusive terminal copper nitrene intermediate. Second, DFT methods were carried out to investigate the mechanism of C–F bond activation by a low-coordinate cobalt(I) complex. The computational models suggested that oxidative addition, which is very rare for 3d metals, was preferred. A π–adduct of PhF was predicted to be a plausible intermediate via calculations. Third, DFT calculations were performed to study ancillary ligand effects on C(sp3)–N bond forming reductive elimination from alkylpalladium(II) amido complexes with different phosphine supporting ligands. The dimerization study of alkylpalladium(II) amido complexes indicated an unique arrangement of dative and covalent Pd-N bonds within the core four-membered ring of bimetallic complexes. In conclusion, computational methods enrich the arsenal of methods available to study catalytic processes in conjunction with experiments.

Over the last 20 years, there has occurred an increase in the number, scope, and impact of nanomaterials projects. By leveraging the Surface Plasmon Resonance of metallic nanoparticles for labelling, sensing, and treatment, researchers have demonstrated the versatile utility of these nanomaterials in medicine. The literature provides evidence of use of simple, well-known chemistry for nanomaterials synthesis when the focus is new applications of nanomaterials. A case in point, is the synthesis of metallic nanoparticles, whereby HAuCl4, CuCl2, Cu(acac)2, and AgNO3 are typically employed as nanoparticle precursors. Unfortunately, the use of these precursors limits the number of applications available to these materials - particularly for AuNPs in medicine, where the byproducts of nanoparticle synthesis (most often surface-adsorbed reductants, toxic stabilizers, and growth directors) cause nanoparticles to fail clinical trials. Despite the several thousand publications detailing the advancements in nanoparticle therapeutics, as of 2017, there were only 50 FDA-approved nanoparticle formulations. Less than 10 were based on metallic nanoparticles. This is a problem because many of these nanoparticle therapeutics demonstrate potent cell killing ability and labeling of cells. A solution to this problem may be the use of weakly coordinated, monovalent metal complexes, which require only one electron to reduce them …

The tetraruthenium cluster H4Ru4(CO)12 has been studied for its reactivity with the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2, 4,5-bis (diphenylphosphino)-4-cyclopenten-1,3-dione, bis(diphenyphosphino)benzene and 1,8- bis(diphenyl phosphino)naphthalene under thermal, near-UV photolysis, and Me3NO-assisted activation. All three cluster activation methods promote loss of CO and furnish the anticipated substitution products that possess a chelating diphosphine ligand. Clusters 1, 2, 3 and 4 have been characterized in solution by IR and NMR spectroscopies, and these data are discussed with respect to the crystallographically determined structures for all new cluster compounds. The 31P NMR spectral data and the solid-state structures confirm the presence of a chelating diphosphine ligand in all four new clusters. Sealed NMR tubes containing clusters 1, 2, 3 and 4 were found to be exceeding stable towards near-UV light and temperatures up to ca. 100°C. The surprisingly robust behavior of the new clusters is contrasted with the related cluster Ru3(CO)10(bpcd) that undergoes fragmentation to the donor-acceptor compound Ru2(CO)6(bpcd) and the phosphido-bridged compound Ru2(CO)6 (µ-PPh2)[µ-C=C(PPh2)C(O)CH2C(O)] under mild conditions. The electrochemical properties have been investigated in the case of clusters 1 and 2 by cyclic voltammetry, and the findings are discussed with respect to the reported electrochemical data on the parent cluster H4Ru4(CO)12.

This work involves synthesis and characterization of isotropic and anisotropic noble metal nanoparticles for applications ranging from antimicrobial uses to anticancer applications. These nanomaterials are stabilized in genuinely benign biomaterials ranging from polymers to cross linked proteins for targeted cancer treatments. The nanoparticles are found to have tunable optical properties.

The effect of substituents on the stabilities of cumulenes-ketenes, allenes, diazomethanes and isocyanates and related systems-alkynes, nitriles and nitrile oxides is studied using the density functional theory (B3LYP, SVWN and BP86) and ab initio (HF, MP2) calculations at the 6-31G* basis set level. Using isodesmic reactions, correlation between stabilization energies of cumulenes and substituent group electronegativities (c BE) is established and the results from DFT and MP2 methods are compared with the earlier HF calculations. Calculations revealed that the density functional methods can be used to study the effect of substituents on the stabilities of cumulenes. It is observed that the cumulenes are stabilized by electropositive substituent groups from s -electron donation and p -electron withdrawal and are destabilized by electronegative substituent groups from n-p donation. The calculated geometries of the cumulenes are compared with the available experimental data.High level ab initio and density functional theory calculations have been used to study the energetics of low-barrier hydrogen bond (LBHB) systems. Using substituted formic acid-formate anion complexes as model LBHB systems, hydrogen bond strength is correlated to the pKa mismatch between the hydrogen bond donor and the hydrogen bond acceptor. LBHB model systems are characterized by the 1H-NMR chemical shift calculations. …

Porphyrins offer a very synthetically flexible template which can be modified in numerous ways to synthesize molecules with very useful properties applicable in areas such as non-linear optical properties, photodynamic therapy, dye-sensitized solar cells, chemical sensors and organic electronic devices. β-Substituted π-extended porphyrins offer unique capabilities in tuning the properties of the molecule towards practical applications. Increased π-conjugation allows the HOMO-LUMO gap to decrease and hence to redshift the absorption into the near-IR region. β-Fused benzoporphyrins offer additional benefits in which the benzene ring itself can be further modified using electron donating substituents and electron donating substituents to electronically tune these porphyrins for various uses. The goal of the research pursued in this dissertation was to develop new methods for the development of β-Substituted π-extended porphyrins and to study their optical and electronic properties. To accomplish this goal, we developed new method to synthesize A2B2 type tetrabenzoporphyrins and we studied the electron transfer in such systems. We also studied the effectiveness of such systems in dye sensitized solar cells. A new method to synthesize functionalized naphthalene fused porphyrins was also developed and we were also able to use this method to synthesize a push-pull naphthalene fused porphyrin.

An iodine surface layer has been prepared on Ru(poly) and Ru(0001) electrodes by exposure to iodine vapor in UHV and polarizing in a 0.1 M HClO4/0.005 M KI solution, respectively. A saturation coverage of I on a Ru(poly) electrode passivates the Ru surface against significant hydroxide, chemisorbed oxygen or oxide formation during exposure to water vapor over an electrochemical cell in a UHV-electrochemistry transfer system. Immersion of I-Ru(poly) results in greater hydroxide and chemisorbed oxygen formation than water vapor exposure, but an inhibition of surface oxide formation relative that of the unmodified Ru(poly) surface is still observed. Studies with combined electrochemical and XPS techniques show that the iodine surface adlayer remained on top of the surface after cycles of overpotential electrodeposition/dissolution of copper on both Ru(poly) and Ru(0001) electrodes. These results indicate the potential bifunctionality of iodine layer to both passivate the Ru surface in the microelectronic processing and to act as a surfactant for copper electrodeposition. The electrodeposition of Cu on Ru(0001) or polycrystalline Ru was studied using XPS with combined ultrahigh vacuum/electrochemistry methodology (UHV-EC) in 0.1 M HClO4 with Cu(ClO4)2 concentrations ranging from 0.005 M to 0.0005 M, and on polycrystalline Ru in a 0.05M H2SO4/0.005 M CuSO4/0.001 …

The ability to passivate metallic surfaces under non-UHV conditions is not only of fundamental interests, but also of growing practical importance in catalysis and microelectronics. In this work, the passivation effect of a surface iodine layer on air-exposed Ta for the copper electroless deposition was investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Although the passivation effect was seriously weakened by the prolonged air exposure, iodine passivates the Ta substrate under brief air exposure conditions so that enhanced copper wetting and adhesion are observed on I-passivated Ta relative to the untreated surface.

An NMR spectroscopy study of trimethylsilylmethyllilthium, TMSM-Li, indicates that TMSM-Li exists as two different aggregates in cyclopentane solution. Using previously reported colligative properties of TMSM-Li in different solutions in connection with new 13C and 6Li NMR data collected in this study, aggregation states were assigned as octamer and hexamer. Low temperature 13C and 6Li NMR peak intensities indicated an equilibrium exists between the two aggregates that shifts toward the octamer as the temperature decreases. ΔH was calculated to be 5.23 + 0.15 kcal/mol and ΔS was calculated to be 17.9 + 0.6 eu for the hexamer/octamer equilibrium system. Samples of TMSM-Li were mixed with TMSM-OH in attempts to form mixed alkyllithium/lithium alkoxide aggregates. 13C NMR data for these mixtures gave inconclusive results whether or not these compounds formed, which is different from other primary alkyllithium compounds studied in the past. A study of neopentyllithium, NpLi, indicates only one aggregate in solution with the aggregation state unknown using low temperature 13C NMR spectroscopy.

To form Cu interconnects, dual-damascene techniques like chemical mechanical planarization (CMP) and post-CMP became inevitable for removing the "overburden" Cu and for planarizing the wafer surface. During the CMP processing, Cu interconnects and barrier metal layers experience different electrochemical interactions depending on the slurry composition, pH, and ohmic contact with adjacent metal layers that would set corrosion process. Ruthenium as a replacement of existing diffusion barrier layer will require extensive investigation to eliminate or control the corrosion process during CMP and post CMP. Bimetallic corrosion process was investigated in the ammonium citrate (a complexing agent of Cu in CMP solutions) using micro test patterns and potentiodynamic measurements. The enhanced bimetallic corrosion of copper observed is due to noble behavior of the ruthenium metal. Cu formed Cu(II)-amine and Cu(II)-citrate complexes in alkaline and acidic solutions and a corrosion mechanism has been proposed. The currently used metallization process (PVD, CVD and ALD) require ultra-high vacuum and are expensive. A novel method of Si surface metallization process is discussed that can be achieved at room temperature and does not require ultra-high vacuum. Ruthenation of Si surface through strong Si-Ru covalent bond formation is demonstrated using different ruthenium carbonyl compounds. RBS analysis accounted for …