We report the synthesis, interconversions and X-ray structures of a set of [mFe-nS]-type carbonyl clusters (where S = S, S or RS; m = 2-3; n = 1-2). All of the clusters have been identified and characterized by single crystal X-ray diffraction, IR and C NMR. Reduction of the parent neutral dimer [μ-(SPh)Fe(CO)] (1) with KC affords an easily separable ∼1 : 1 mixture of the anionic, dimeric thiolate dimer K[Fe(SPh)(CO)(μ-CO)] (2) and the dianionic, sulfido trimer [K(benzo-15-crown-5)][Fe(μ-S)(CO)] (3). Oxidation of 2 with diphenyl-disulfide (PhS) cleanly returns the starting material 1. The Ph-S bond in 1 can be cleaved to form sulfide trimer 3. Oxidation of sulfido trimer 3 with [Fc](PF) in the presence of S cleanly affords the all-inorganic persulfide dimer [μ-(S)Fe(CO)] (4), a thermodynamically stable product. The inverse reactions to form 3 (dianion) from 4 (neutral) were not successful, and other products were obtained. For example, reduction of 4 with KC afforded the mixed valence Fe(i)/Fe(ii) species [((FeS)(CO))Fe] (5), in which the two {FeS(CO)} units serve as bidendate ligands to a Fe(ii) center. Another isolated product (THF insoluble portion) was recrystallized in MeCN to afford [K(benzo-15-crown-5)][((FeS)(CO))(μ-S)] (6), in which a persulfide dianion bridges two {2Fe-S} moieties (dimer of dimers). Finally, to close the interconversion loop, we converted the persulfide dimer 4 into the thiolate dimer 1 by reduction with KC followed by reaction with the diphenyl iodonium salt [PhI](PF), in modest yield. These reactions underscore the thermodynamic stability of the dimers 1 and 4, as well as the synthetic and crystallization versatility of using the crown/K counterion system for obtaining structural information on highly reduced iron-sulfur-carbonyl clusters.
Aminoindanes are one class of many new psychoactive substances that have emerged over the last decade. Analogues of 2-aminoindane (2-AI) are being encountered in crime laboratories and analytical data for most aminoindanes are limited. Interpretation and optimization of gas chromatography-mass spectrometry data will enhance reliability in characterizing aminoindanes. Methods: This study focuses on the electron ionization mass spectrometric fragmentation of eight aminoindane analogues and the gas chromatographic separation of these eight aminoindane analogues using four different column stationary phases, Rxi ® -1Sil MS, Rxi ® -5Sil MS, Rxi ® -35Sil MS, and Rxi ® -624Sil MS. Split injection (25:1) was utilized and each column had the same configuration (30 m  25 mm  0.25 μm), with the exception of the Rxi ® -624Sil MS column (30 m  25 mm Â1.4 μm).Results: Mass spectra showed strong molecular ions for all aminoindanes, except for rasagiline that produced a uniquely abundant [M À 1] ion. Other characteristic fragmentation that was present for all the aminoindanes included indane and indene ions (m/z 115-117), the tropylium ion (m/z 91), and subsequent loss of diene to produce smaller ions that followed: phenyl (m/z 77), cyclopentadienyl (m/z 65), cyclobutadienyl (m/z 51), and cyclopropenyl (m/z 39).Conclusions: Separation of eight aminoindanes was optimized, and linear retention indices were determined for the compounds on four capillary columns. Based on the retention data, all eight aminoindanes were resolved on an Rxi ® -624Sil MS column.Each aminoindane exhibited unique fragmentation ions in the mass spectra to distinguish between similar analogues. The results of this study will strengthen the analytical profiles of 2-AI and seven analogues, assisting forensic scientists in their analysis and identification of these substances. | INTRODUCTIONNew psychoactive substances (NPSs) continue to rise in number and variety, which poses a threat to public safety and creates a demand for drug legislation expansion. 1,2 These compounds may produce effects similar to those of traditional illicit substances or have effects that are unexpected and unpredictable. NPSs are made with the intention of evading existing drug control laws, which is why they are
Aminoindanes are a class of novel psychoactive substances (NPSs) that have become more prevalent over the past decade. GC–MS is often utilized for identifying seized drugs and is well regarded for its ability to separate mixtures. However, certain aminoindanes have similar mass spectral data and require specific gas chromatographic stationary phases for separation. Derivatization is an alternative method that can be applied to GC–MS to enhance chromatographic results, providing more selective analysis in seized‐drug identification. This study investigates derivatization techniques to provide options for forensic science laboratories in accurately identifying aminoindanes. Three derivatization reagents, N‐methyl‐bis(trifluoroacetamide) (MBTFA), heptafluorobutyric anhydride (HFBA), and ethyl chloroformate (ECF) were evaluated for the analysis of eight aminoindanes by GC–MS using two common gas chromatographic stationary phases, Rxi®‐5Sil MS and Rxi®‐1Sil MS. All three derivatization methods successfully isolated eight aminoindanes, including the isomers 4,5‐methylenedioxy‐2‐aminoindane (4,5‐MDAI), and 5,6‐methylenedioxy‐2‐aminoindane (5,6‐MDAI) that could not be differentiated prior to derivatization. Reduced peak tailing and increased abundance were observed after derivatization for all the compounds, and mass spectra of the derivatives contained individualizing fragment ions that allowed for further characterization of the aminoindanes. This excluded 4,5‐MDAI and 5,6‐MDAI as they shared the same characteristic ions and were only distinguishable by their retention times. All three derivatization techniques used in this study allow for successful characterization of the aminoindanes and give forensic science laboratories flexibility in their analysis approach when they encounter these compounds.
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