Organometallic Ions Research Articles

Mass spectrometry and in situ x-ray photoelectron spectroscopy investigations of organometallic species induced by the etching of germanium, antimony and selenium in a methane-based plasma

Organometallic positive ions were identified in inductively coupled plasmas by means of mass spectrometry during the etching of Ge, Sb, Se materials. A preliminary study was focused on identifying M x H y + (M = Ge, Sb, Se) positive ion clusters during a H2/Ar etching process. The methane addition to the H2/Ar mixture generates CH x reactive neutral species. The latter react with the metalloids within gas phase to form M x C y H z + organometallic ions. In addition, the etching of Sb2Se3 and Ge19.5Sb17.8Se62.7 bulk targets forms mixed products via ion-molecule reactions as evidenced by the presence of SeSbC x H y + ion clusters. Changes in surface composition induced by the newly formed organometallic structures were investigated using in situ x-ray photoelectron spectroscopy. In the case of the Ge and Sb surfaces, (M)–M–C x environments broadened the Ge 2p3/2, Ge 3d, Sb 3d and Sb 4d spectra to higher values of binding energy. For the Se surface, only the hydrogen and methyl bonding could explain the important broadening of the Se 3d core level. It was found that the Ge39Se61 thin film presents an induced (Ge)–Ge–Se entity on the Ge 2p3/2 and Ge 3d core levels.

Gas-phase formation of Grignard-type organolanthanide (III) ions RLnCl3 - : The influences of lanthanide center and hydrocarbyl group.

Compared with organomagnesium compounds (Grignard reagents), the Grignard-type organolanthanides (III) exhibit several utilizable differences in reactivity. However, the fundamental understanding of Grignard-type organolanthanides (III) is still in its infancy. Decarboxylation of metal carboxylate ions is an effective method to obtain organometallic ions that are well suited for gas-phase investigation using electrospray ionization (ESI) mass spectrometry in combination with density functional theory (DFT) calculations. The (RCO2 )LnCl3 - (R = CH3 , Ln = La-Lu except Pm; Ln = La, R = CH3 CH2 , CH2 CH, HCC, C6 H5 , and C6 H11 ) precursor ions were produced in the gas phase via ESI of LnCl3 and RCO2 H or RCO2 Na mixtures in methanol. Collision-induced dissociation (CID) was employed to examine whether the Grignard-type organolanthanide (III) ions RLnCl3 - can be obtained via decarboxylation of lanthanide chloride carboxylate ions (RCO2 )LnCl3 - . DFT calculations can be used to determine the influences of lanthanide center and hydrocarbyl group on the formation of RLnCl3 - . When R = CH3 , CID of (CH3 CO2 )LnCl3 - (Ln = La-Lu except Pm) yielded decarboxylation products (CH3 )LnCl3 - and reduction products LnCl3 ·- with a variation in the relative intensity ratio of (CH3 )LnCl3 - /LnCl3 ·- . The trend is as follows: (CH3 )EuCl3 - /EuCl3 ·- < (CH3 )YbCl3 - /YbCl3 ·- ≈ (CH3 )SmCl3 - /SmCl3 ·- < other (CH3 )LnCl3 - /LnCl3 ·- , which complies with the trend of Ln (III)/Ln (II) reduction potentials in general. When Ln = La and hydrocarbyl groups were varied as CH3 CH2 , CH2 CH, HCC, C6 H5 , and C6 H11 , the fragmentation behaviors of these (RCO2 )LaCl3 - precursor ions were diverse. Except for (C6 H11 CO2 )LaCl3 - , the four remaining (RCO2 )LaCl3 - (R = CH3 CH2 , CH2 CH, HCC, and C6 H5 ) ions all underwent decarboxylation to yield RLaCl3 - . (CH2 CH)LaCl3 - and especially (CH3 CH2 )LaCl3 - are prone to undergo β-hydride transfer to form LaHCl3 - , whereas (HCC)LaCl3 - and (C6 H5 )LaCl3 - are not. A minor reduction product, LaCl3 ·- , was formed via C6 H5 radical loss of (C6 H5 )LaCl3 - . The relative intensities of RLaCl3 - compared to (RCO2 )LaCl3 - decrease as follows: HCC > CH2 CH > C6 H5 > CH3 > CH3 CH2 >> C6 H11 (not visible). A series of Grignard-type organolanthanide (III) ions RLnCl3 - (R = CH3 , Ln = La-Lu except Pm; Ln = La, R = CH3 CH2 , CH2 CH, HCC, and C6 H5 ) were produced from (RCO2 )LnCl3 - via CO2 loss, whereas (C6 H11 )LaCl3 - did not. The experimental and theoretical results suggest that the reduction potentials of Ln (III)/Ln (II) couples as well as the bulkiness and hybridization of hydrocarbyl groups play important roles in promoting or limiting the formation of RLnCl3 - via decarboxylation of (RCO2 )LnCl3 - .

Highly Electrocatalytic Conversion and Separation of Organometallic Ions to Vapor on an Au-Modified Nickel Foam Cathode: A Classic Application for Mercury Speciation Analysis at the μg/L Level

A simple, accurate, and sustainable electrocatalytic conversion strategy has been used for the speciation analysis of trace mercury. An Au- or Ag-modified nickel foam electrode (Au/NFE or Ag/NFE) prepared by cyclic voltammetry was used first as a cathode for the gaseous conversion of organomercury. The mechanism of improving the electrochemical inertness of methylmercury is considered to be the migration of charge centers and the weakening of C–Hg bonds caused by the formation of Au–Hg amalgam. A large specific surface area, high catalytic activity, and low transport resistance allow an effective conversion of 0.1 μg L–1 level organomercury on the Au/NFE surface. The difference of gaseous conversion behavior under current control also provides a green way for the analysis of mercury speciation. A lower limit of detection (4.9 pg g –1 for Hg2+ and 5.5 pg g –1 for CH3Hg+), stronger anti-interference ability, more than 180 sample analysis capacities, and less than 8% signal fluctuation, importantly, confirmed that the electrocatalytic conversion technology based on the gold/silver-modified NFE is very suitable for the analysis of ultratrace methylmercury in complex matrix samples, such as animal and plant samples.

Application of continuous wave quantum cascade laser in combination with CIVP spectroscopy for investigation of large organic and organometallic ions.

Rapidly developing mid-infrared quantum cascade laser (QCL) technology gives easy access to broadly tunable mid-IR laser radiation at a modest cost. Despite several applications of QCL in the industry, its usage for spectroscopic investigation of synthetically relevant organic compounds has been limited. Here, we report the application of an external cavity, continuous wave, mid-IR QCL to cryogenic ion vibrational predissociation spectroscopy to analyze a set of large organic molecules, organometallic complexes, and isotopically labeled compounds. The obtained spectra of test molecules are characterized by a high signal-to-noise ratio and low full width at half-maximum-values, allowing the assignment of two compounds with just a few wavenumber difference. Data generated by cw-QCL and spectra produced by another standard Nd:YAG difference-frequency generation system are compared and discussed.

Bioorganometallic Compounds as Novel Drug Targets against Schistosomiasis in Sub-Saharan Africa: An alternative to Praziquantel?

Human schistosomiasis is a disease that mostly plagues the destitute of various tropical and sub-tropical countries, particularly in sub-Saharan Africa (SSA) and South America. It has significant effects on various health and economic-related matters. Globally, the burden of schistosomiasis has been controlled with a single chemotherapeutic drug, praziquantel (PZQ), which has recently demonstrated several clinical issues, including its inability to destroy juvenile schistosome worms and drug resistance because of its extensive use. The use of organometallic moieties in biological and medicinal chemistry has developed greatly and has led to their use in various anti-cancer and anti-infectious agents. The abundance of a range of organometallic compounds that can cause damage to the parasite has received tremendous feedback, with many already at clinical trials. The distinct redox biology of the schistosome parasite is a vulnerable element to the survival of the worm and has steered attempts toward the use of redox-directed bioorganometallic compounds. Disruption of the schistosome redox homeostasis through organometallic ions provides a novel drug target that could be used in overcoming the drawbacks of the mainstream drug and one that could possibly bypass the emergence of drug resistance.

Tuning Vibrational Strong Coupling with Co-Resonators

Strong coupling of molecular vibrations to optical resonances is a promising route toward photonic control over chemical reactions. Due to their narrow line widths and close energy proximity, vibrational transitions afford intriguing opportunities for strong coupling of multiple matter states with the same optical state to form polaritons with significant hybridization. Solutions of three organometallic ions were used to control the number, energy, and intensity of molecular resonances in a 200 cm–1 window, allowing for a systematic investigation of the formation of three, four, and five polaritons. The presence of additional molecules simultaneously coupled to an optical mode did not significantly affect the Rabi splitting energy of a given molecular resonance, but did substantially alter the Hopfield mixing coefficients of the resulting polaritons. The introduction of a co-resonator is therefore an alternative means for the modification of the properties of polaritons.

Binding mechanisms of half-sandwich Rh(III) and Ru(II) arene complexes on human serum albumin: a comparative study

Various half-sandwich ruthenium(II) arene complexes and rhodium(III) arene complexes have been intensively investigated due to their prominent anticancer activity. The interaction of the organometallic complexes of Ru(η6-p-cymene) and Rh(η5-C5Me5) with human serum albumin (HSA) was studied in detail by a combination of various methods such as ultrafiltration, capillary electrophoresis, 1H NMR spectroscopy, fluorometry and UV–visible spectrophotometry in the presence of 100 mM chloride ions. Binding characteristics of the organometallic ions and their complexes with deferiprone, 2-picolinic acid, maltol, 6-methyl-2-picolinic acid and 2-quinaldic acid were evaluated. Kinetic aspects and reversibility of the albumin binding are also discussed. The effect of low-molecular-mass blood components on the protein binding was studied in addition to the interaction of organorhodium complexes with cell culture medium components. The organometallic ions were found to bind to HSA to a high extent via a coordination bond. Release of the bound metal ions was kinetically hindered and could not be induced by the denaturation of the protein. Binding of the Ru(η6-p-cymene) triaqua cation was much slower (ca. 24 h) compared to the rhodium congener (few min), while their complexes interacted with the protein relatively fast (1–2 h). The studied complexes were bound to HSA coordinatively. The highly stable and kinetically inert 2-picolinate Ru(η6-p-cymene) complex bound in an associative manner preserving its original entity, while lower stability complexes decomposed partly or completely upon binding to HSA. Fast, non-specific and high-affinity binding of the complexes on HSA highlights their coordinative interaction with various types of proteins possibly decreasing effective drug concentration.Graphic abstract

ChemInform Abstract: Gas‐Phase Studies of Metal Catalyzed Decarboxylative Cross‐Coupling Reactions of Esters

AbstractReview: 91 refs.

ChemInform Abstract: Gas Phase Studies of the Pesci Decarboxylation Reaction: Synthesis, Structure, and Unimolecular and Bimolecular Reactivity of Organometallic Ions

AbstractReview: 67 refs.

Gas-phase studies of metal catalyzed decarboxylative cross-coupling reactions of esters

Abstract Metal-catalyzed decarboxylative coupling reactions of esters offer new opportunities for formation of C–C bonds with CO2 as the only coproduct. Here I provide an overview of: key solution phase literature; thermochemical considerations for decarboxylation of esters and thermolysis of esters in the absence of a metal catalyst. Results from my laboratory on the use of multistage ion trap mass spectrometry experiments and DFT calculations to probe the gas-phase metal catalyzed decarboxylative cross-coupling reactions of allyl acetate and related esters are then reviewed. These studies have explored the role of the metal carboxylate complex in the gas phase decarboxylative coupling of allyl acetate proceeding via a simple two-step catalytic cycle. In Step 1, an organometallic ion, [CH3ML]+/– (where M is a group 10 or 11 metal and L is an auxillary ligand), is allowed to undergo ion-molecule reactions with allyl acetate to generate 1-butene and the metal acetate ion, [CH3CO2ML]+/–. In Step 2, the metal acetate ion is subjected to collision-induced dissociation to reform the organometallic ion and thereby close the catalytic cycle. DFT calculations have been used to explore the mechanisms of these reactions. The organometallic ions [CH3CuCH3]–, [CH3Cu2]+, [CH3AgCu]+ and [CH3M(phen)]+ (where M = Ni, Pd and Pt) all undergo C–C bond coupling reactions with allyl acetate (Step 1), although the reaction efficiencies and product branching ratios are highly dependant on the nature of the metal complex. For example, [CH3Ag2]+ does not undergo C–C bond coupling. Using DFT calculations, a diverse range of mechanisms have been explored for these C–C bond-coupling reactions including: oxidative-addition, followed by reductive elimination; insertion reactions and SN2-like reactions. Which of these mechanisms operate is dependant on the nature of the metal complex. A wide range of organometallic ions can be formed via decarboxylation (Step 2) although these reactions can be in competition with other fragmentation channels. DFT calculations have located different types of transition states for the formation of [CH3CuCH3]–, [CH3Cu2]+, [CH3AgCu]+ and [CH3M(phen)]+ (where M = Ni, Pd and Pt). Of the catalysts studied to date, [CH3Cu2]+ and [CH3Pd(phen)]+ are best at promoting C–C bond formation (Step 1) as well as being regenerated (Step 2). Preliminary results on the reactions of [C6H5M(phen)]+ (M = Ni and Pd) with C6H5CO2CH2CH=CH2 and C6H5CO2CH2C6H5 are described.

Gas phase studies of the Pesci decarboxylation reaction: synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions.

CONSPECTUS: Decarboxylation chemistry has a rich history, and in more recent times, it has been recruited in the quest to develop cheaper, cleaner, and more efficient bond-coupling reactions. Thus, over the past two decades, there has been intense investigation into new metal-catalyzed reactions of carboxylic substrates. Understanding the elementary steps of metal-mediated transformations is at the heart of inventing new reactions and improving the performance of existing ones. Fortunately, during the same time period, there has been a convergence in mass spectrometry (MS) techniques, which allows these catalytic processes to be examined efficiently in the gas phase. Thus, electrospray ionization (ESI) sources have been combined with ion-trap mass spectrometers, which in turn have been modified to either accept radiation from tunable OPO lasers for spectroscopy based structural assignment of ions or to allow the study of ion-molecule reactions (IMR). The resultant "complete" gas-phase chemical laboratories provide a platform to study the elementary steps of metal-catalyzed decarboxylation reactions in exquisite detail. In this Account, we illustrate how the powerful combination of ion trap mass spectrometry experiments and DFT calculations can be systematically used to examine the formation of organometallic ions and their chemical transformations. Specifically, ESI-MS allows the transfer of inorganic carboxylate complexes, [RCO2M(L)n](x), (x = charge) from the condensed to the gas phase. These mass selected ions serve as precursors to organometallic ions [RM(L)n](x) via neutral extrusion of CO2, accessible by slow heating in the ion trap using collision induced dissociation (CID). This approach provides access to an array of organometallic ions with well-defined stoichiometry. In terms of understanding the decarboxylation process, we highlight the role of the metal center (M), the organic group (R), and the auxiliary ligand (L), along with cluster nuclearity, in promoting the formation of the organometallic ion. Where isomeric organometallic ions are generated and normal MS approaches cannot distinguish them, we describe approaches to elucidate the decarboxylation mechanism via determination of their structure. These "unmasked" organometallic ions, [RM(L)n](x), can also be structurally interrogated spectroscopically or via CID. We have thus compared the gas-phase structures and decomposition of several highly reactive and synthetically important organometallic ions for the first time. Perhaps the most significant aspect of this work is the study of bimolecular reactions, which provides experimental information on mechanistically obscure bond-formation and cross-coupling steps and the intrinsic reactivity of ions. We have sought to understand transformations of substrates including acid-base and hydrolysis reactions, along with reactions resulting in C-C bond formation. Our studies also allow a direct comparison of the performance of different metal catalysts in the individual elementary steps associated with protodecarboxylation and decarboxylative alkylation cycles. Electronic structure (DFT and ab initio) and dynamics (RRKM) calculations provide further mechanistic insights into these reactions. The broad implications of this research are that new reactions can be discovered and that the performance of metal catalysts can be evaluated in terms of each of their elementary steps. This has been particularly useful for the study of metal-mediated decarboxylation reactions.

In situ SIMS and IR spectroscopy of well-defined surfaces prepared by soft landing of mass-selected ions.

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3](2+) (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.

Synthesis and Catalytic Reactions of Nanoparticles formed by Electrospray Ionization of Coinage Metals

AbstractNoble metals can be ionized by electrochemical corrosion and transported by electrospray ionization. Mass spectrometry (MS) showed solvated metal ions as the main ionic constituent of the sprayed droplets. Collection of the electrospray plume on a surface yielded noble metal nanoparticles (NPs) under ambient conditions. The NPs were characterized by several techniques. Under typical conditions, capped‐nanoparticle sizes averaged 2.2 nm for gold and 6.5 nm for silver. The gold nanoparticles showed high catalytic activity in the reduction of p‐nitrophenol by NaBH4. Efficient catalysis was also observed by simply directing the spray of solvated Au+ onto the surface of an aqueous p‐nitrophenol/NaBH4 mixture. Organometallic ions were generated by spiking ligands into the spray solvent: for example, CuI bipyridine cations dominated the spray during Cu electrocorrosion in acetonitrile containing bipyridine. This organometallic reagent was shown to be effective in the radical polymerization of styrene.

Synthesis and Catalytic Reactions of Nanoparticles formed by Electrospray Ionization of Coinage Metals

Noble metals can be ionized by electrochemical corrosion and transported by electrospray ionization. Mass spectrometry (MS) showed solvated metal ions as the main ionic constituent of the sprayed droplets. Collection of the electrospray plume on a surface yielded noble metal nanoparticles (NPs) under ambient conditions. The NPs were characterized by several techniques. Under typical conditions, capped-nanoparticle sizes averaged 2.2 nm for gold and 6.5 nm for silver. The gold nanoparticles showed high catalytic activity in the reduction of p-nitrophenol by NaBH4 . Efficient catalysis was also observed by simply directing the spray of solvated Au(+) onto the surface of an aqueous p-nitrophenol/NaBH4 mixture. Organometallic ions were generated by spiking ligands into the spray solvent: for example, Cu(I) bipyridine cations dominated the spray during Cu electrocorrosion in acetonitrile containing bipyridine. This organometallic reagent was shown to be effective in the radical polymerization of styrene.

Fixed-charge phosphine ligands to explore gas-phase coinage metal-mediated decarboxylation reactions

A combination of multistage mass spectrometry experiments and density functional theory (DFT) calculations were used to examine the decarboxylation reactions of a series of metal carboxylate complexes bearing a fixed-charge phosphine ligand, [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph). Collision-induced dissociation (CID) of these complexes using an LTQ linear ion mass spectrometer results in three main classes of reactions being observed: (1) decarboxylation; (2) loss of the phosphine ligand; (3) loss of carboxylic acid. The gas-phase unimolecular chemistry of the resultant decarboxylated organometallic ions, [(O3SC6H4)(C6H5)2PM(I)R](-), were also explored using CID experiments, and fragment primarily via loss of the phosphine ligand. Energy-resolved CID experiments on [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph) using a Q-TOF mass spectrometer were performed to gain a more detailed understanding of the factors influencing coinage metal-catalyzed decarboxylation and DFT calculations on the major fragmentation pathways aided in interpretation of the experimental results. Key findings are that: (1) the energy required for loss of the phosphine ligand follows the order Ag < Cu < Au; (2) the ease of decarboxylation of the coordinated RCO2 groups follows the order of R: Ph < PhCH2 < Me < Et; (3) in general, copper is best at facilitating decarboxylation, followed by gold then silver. The one exception to this trend is when R = Ph and M = Au which has the highest overall propensity for decarboxylation. The influence of the phosphine ligand on decarboxylation is also considered in comparison with previous studies on metal carboxylates that do not contain a phosphine ligand.

Gas-Phase Unimolecular Reactions of Pallada- and Nickelalactone Anions

Electrospray ionization in combination with multistage mass spectrometry experiments in a linear ion trap mass spectrometer was used to generate and study the gas-phase ion chemistry of the metallalactones [(CH3CO2)Ni(CH2CO2)]− (m/z 175, 5a) and [(CH3CO2)Pd(CH2CO2)]− (m/z 223, 5b). Low-energy collision-induced dissociation (CID) resulted in decarboxylation to produce novel organometallic ions at m/z 131 (Ni) and m/z 179 (Pd). Isotope labeling experiments, bimolecular gas-phase reactions with allyl iodide, and DFT calculations reveal that decarboxylation primarily occurs from the acetato ligand to yield ions of the form [(CH3)M(CH2CO2)]− (M = Pd, Ni). Further CID experiments on [(CH3)M(CH2CO2)]− together with DFT calculations highlight the following. (1) Both palladium and nickel can facilitate C–C bond formation, with elimination of ethylene being observed. (2) The mechanism for formation of ethylene from [(CH3)M(CH2CO2)]− is inherently different for M = Pd versus M = Ni. Elimination of ethylene is compet...

Heavy Metallic and Organometallic Ions Scavenging Using Silica‐Based Adsorbent Functionalized with Ligands Containing Sulfur and Nitrogen Elements

AbstractA variety of silica‐based solid phases, whose surfaces are functionalized with ligands containing sulfur and nitrogen elements, are used as self‐supporting adsorbents for environmental remediation evaluation and potential separation application. Each adsorbent is tested for its ability to scavenge five metallic ions: Hg2+, Cu2+, Cd2+, Mn2+, Pb2+, and two organometallic ions: ethylmercury and phenylmercury, from independent homoionic solutions at both neutral and acidic pH values. The results indicate that the percentage of these ions scavenged by a given adsorbent varies, and is found to be highly related to the structural environment in the vicinity of the sulfur and nitrogen elements on the ligand. It is believed that the scavenging of metallic ions is a result of the complexation formation between the metallic ions and the ligands containing sulfur and nitrogen elements, and is not due to the irreversible association chemistry with the sulfur or nitrogen element itself. In the case of organometallic ions, a π‐π interaction is thought to be involved in the adsorption with ligands containing an aromatic moiety in addition to the aforementioned forces. The time needed to reach the maximum percent of adsorption decreases as the amount of adsorbent increases. The longer the adsorption time, the higher percent of ion is removed. Other factors, such as the temperature and the acidity in the liquid phase of the matrix affect the percentage of ions scavenged as well.

Structural analysis of organometallic compounds with soft ionization mass spectrometry

The analysis of organometallic compounds with mass spectrometry has some special features in comparison with organic and bioorganic compounds. The first step is the choice of a suitable ionization technique, where the electrospray ionization is certainly the best possibility for most classes of organometallic compounds and metal complexes. Some ionization mechanisms of organometallic compounds are comparable to organic molecules, such as protonation/deprotonation, and adduct formation with sodium or potassium ions; however, in many cases, different mechanisms and their combinations complicate the spectra interpretation. Organometallics frequently undergo various types of adduct and polymerization reactions that result in significantly higher masses observed in the spectra in comparison to molecular weights of studied compounds. Metal elements typically have more natural isotopes than common organic elements, which cause characteristic wide distributions of isotopic peaks; for example, tin has ten natural isotopes. The isotopic pattern can be used for the identification of the type and number of metal elements in particular ions. The ionization and fragmentation behavior also depend on the type of metal atom; therefore, our discussion of mass spectra interpretation is divided according to the different type of organometallic compounds. Among various types of mass spectrometers available on the market, trap-based analyzers (linear or spherical ion-traps, Orbitrap) are suitable to study complex fragmentation pathways of organometallic ions and their adducts, whereas high-resolution and high-mass accuracy analyzers (time-of-flight-based analyzers, or Fourier transform-based analyzers-Orbitrap or ion cyclotron resonance mass spectrometers) provide accurate masses applicable for the determination of the elemental composition of individual ions.

Group theory and reaction mechanisms: An extension of the mciver-stanton rules

McIver and Stanton's rules concerning the symmetry of transition states have a counterpart in rules concerning the permutation symmetry of single steps in degenerate rearrangements, derivable with the aid of Longuet-Higgins group theory. Examples in organometallic fluxional systems and carbonium ions illustrate the rules; the analysis leads to prediction of hitherto unexplored pathways for rearrangements in ethyl and homotetrahedryl cations.

Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

The gas-phase reactivity of doubly charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly charged organometallic ions-adducts or species formed via metal ion induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons-and singly charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.