RESUMO
The detection of intact explosives in the field provides a unique challenge for investigators, considering the sensitive and dangerous nature of these samples. Handheld Raman instruments have grown in popularity for the analysis of unknown samples in the field, combining speed of data collection and reliability with a size that allows for the instruments to be field portable. Handheld Raman instruments are used commonly in the field, and yet there is very little research on the detection capabilities of these instruments, specifically for explosive compounds. The present study aimed to evaluate the detection capabilities of two handheld Raman spectrometers, the Rigaku ResQ-CQL and the Field Forensics HandyRam™, using explosives analytical standards, including 2,4,6-trinitrotoluene (TNT), nitromethane (NM), ammonium nitrate (AN) and smokeless powder components such as diphenylamine (DPA), ethyl centralite (EC), and methyl centralite (MC). The spectrometers were evaluated on their sensitivity, the repeatability of the data, and the performance of the internal library when available. In addition, an interference study with glass and plastic containers was also performed. Finally, authentic intact explosive samples, including TNT flakes, a mixture of ammonium nitrate and fuel oil (ANFO), smokeless powder and nitromethane were analyzed to evaluate the developed method and test the detection capabilities of the spectrometers with authentic samples. Spectra were reproducible for all the analytes across both instruments, with regards to the peak location and the intensity. Spectra obtained with the Rigaku ResQ-CQL displayed better resolution for all analytes, including the authentic samples. In addition, its wider scan range allowed for the detection of more detailed peaks below 400 cm-1. Identifying the detection capabilities of these handheld instruments can therefore help guide investigators on how to best utilize them in the field.
RESUMO
The mononuclear cobalt hydride complex [HCo(triphos)(PMe3)], in which triphos = PhP(CH2CH2PPh2)2, was synthesized and characterized by X-ray crystallography and by 1H and 31P NMR spectroscopy. The geometry of the compound is a distorted trigonal bipyramid in which the axial positions are occupied by the hydride and the central phosphorus atom of the triphos ligand, while the PMe3 and terminal triphos donor atoms occupy the equatorial positions. Protonation of [HCo(triphos)(PMe3)] generates H2 and the Co(I) cation, [Co(triphos)(PMe3)]+, and this reaction is reversible under an atmosphere of H2 when the proton source is weakly acidic. The thermodynamic hydricity of HCo(triphos)(PMe3) was determined to be 40.3 kcal/mol in MeCN from measurements of these equilibria. The reactivity of the hydride is, therefore, well suited to CO2 hydrogenation catalysis. Density functional theory (DFT) calculations were performed to evaluate the structures and hydricities of a series of analogous cobalt(triphosphine)(monophosphine) hydrides where the phosphine substituents are systematically changed from Ph to Me. The calculated hydricities range from 38.5 to 47.7 kcal/mol. Surprisingly, the hydricities of the complexes are generally insensitive to substitution at the triphosphine ligand, as a result of competing structural and electronic trends. The DFT-calculated geometries of the [Co(triphos)(PMe3)]+ cations are more square planar when the triphosphine ligand possesses bulkier phenyl groups and more tetrahedrally distorted when the triphosphine ligand has smaller methyl substituents, reversing the trend observed for [M(diphosphine)2]+ cations. More distorted structures are associated with an increase in ΔGH-°, and this structural trend counteracts the electronic effect in which methyl substitution at the triphosphine is expected to yield smaller ΔGH-° values. However, the steric influence of the monophosphine follows the normal trend that phenyl substituents give more distorted structures and increased ΔGH-° values.
