Studies in negative ion mass spectrometry. XIII—Electron attachment to a series of Nickel(II) β-diketonate complexes

Results of electron attachment reactions and negative ion mass spectra are presented for a group of selected nickel(II) β-diketonate complexes of formula Ni[R¹COCHCOR²]₂, where R¹ is a perfluoroalkyl group and R² either an alkyl or aryl group. Molecular negative ions together with ligand ions are the major contributors to the total ion currents for each compound, and the degree of fragmentation has been shown to be dependent on the substituents R¹ and R². Fragmentation schemes have been elucidated for all the major ion decomposition pathways, and all significant ions have been identified in the negative ion mass spectra of each compound. Bis(1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionato) nickel(II), with R¹?CF₃ and R²?tert-butyl is the complex which shows considerable potential for analytical quantitation in the negative ion mode, because of the stability of its negative molecular ion, the high negative ion yield given after electron attachment, as well as the volatility of the compound.     

Studies in negative ion mass spectrometry. VII—Negative ion mass spectra of copper (II) β-diketonate complexes

Electron capture processes in a series of copper (II) β-diketonate complexes of formula Cu[R¹COCHCOR²]₂ (where R¹ is an alkyl, perfluoroalkyl or aryl group and R² either an alkyl or aryl group) have been examined. Molecular anions, ligand ions and some novel rearrangement ions have been observed with these compounds. Relative intensities of fragment ions were dependent on the substituents R¹, R² as well as the electron energy and compound pressure in the ion source. By operating the mass spectrometer at compound pressures of c. 4×10^?6 Torr and higher, reproducible negative ion mass spectra (free from any significant ion-molecule contributions) have been obtained for all compounds of the series.     

Studies in negative ion mass spectrometry. VIII—Electron capture by some monomeric and dimeric η5—cylcopentadienyl transition metal carbonyls

The negative ion mass spectra of a series of monomeric and dimeric η⁵-cyclopentadienyl transition metal carbonyls have been examined. The base peak in the case of the monomeric compounds (η⁵-C₅H₅)V(CO)₄, (η⁵-C₅H₅)Mn(CO)₃ and (η⁵-CH₃C₅H₄)Mn(CO)₃ arises from a reductive decarbonylation of the parent molecule—the resulting radical anion [M–CO]^? is formally isoelectronic with the molecular cations [M]^? observed in the positive ion mass spectra of these compounds and subsequently undergoes successive decarbonylations to the ‘aromatic’ cyclopentadienyl anions. For the compound (η⁵-C₅H₅)Co(CO)₂, however, a molecular anion was observed as the base peak which has been formulated as [(η³-C₅H₅)Co(CO)₂]^? in the light of considerations based on the rare gas rule. As expected, the dimeric molecules [(η⁵-C₅H₅)M(CO)₃]₂ (where M = Cr or Mo) and [(η⁵-C₅H₅)Fe(CO)₂]₂ (and its methyl analogue) undergo reductive cleavage of their metal-metal bonds to give the anions [(η⁵-C₅H₅)M(CO)₃]^? and [(η⁵-C₅H₅)Fe(CO)₂]^? as the base peaks in their negative ion mass spectra. The dimeric nickel compound [(η⁵-C₅H₅)Ni(CO)]₂, however, reductively decarbonylates to the [M-CO]^? radical anion as its predominant fragmentation in the gas phase. Very low abundances of [(η⁵-C₅H₅)Fe(CO)₂] and [(η⁵-CH₃C₅H₄)Fe(CO)₂] were also observed.     

Studies in negative ion mass spectrometry. X—Electron capture by a series of tris(hexafluoroacetylacetonato) metal chelates

Results of electron capture and negative ion mass spectrometric studies are reported for a series of tris-chelates of the type Metal. L₃, where L refers to the ligand or enolate ion of the β-diketone 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hexafluoracetylacetone), and the metals are: Sc(III), Ti(III), V(III), Cr(III), Mn(III), Fe(III), Co(III), A1(III), Ga(III), In(III). The negative ion mass spectra were all relatively simple; the most abundant ions being the molecular and ligand ions for all the metals studied. Reaction schemes have been established to account for the appearance of all significant fragment ions, many of which have been formed as a result of fluorine atom transfer processes. For the transition metal complexes, evidence for elimination of neutral divalent metal fluorides comes from the ion decomposition reactions [Metal.L.F₂]^?→[L]^?, and for the Group III metal complexes, [Metal.L₃]^?→[Metal.L₂]^? as well as [Metal.L₂]^?→[L]^? processes indicate that the metals have been reduced as a consequence of the initial electron capture and subsequent fragmentations of metal-containing ions. The influence of the metal atom and its 3d-electron configuration has been shown not to affect significantly the electron capture processes. However, the relative instabilities of molecular anions of the transition metal tris-complexes show an approximately linear dependence on the increasing 3d-electron populations of the metal ions from Ti(III) to Co(III).     

Studies in negative ion mass spectrometry. IX—electron capture by a series of tris- and bis-(dipivaloylmethanato) metal chelates

Electron capture data and negative ion mass spectra are reported for a series of tris- and bis-chelates of the types Metal·L₃, Metal·L₂, where L (or dpm) refers to the ligand or enolate ion of the β-diketone 2,2,6,6-tetramethyl-3,5-heptanedione (dipivaloylmethane) and the metals are: Sc(III), Cr(III), Mn(III), Fe(III), Co(III), Al(III), Ga(III), In(III), Co(II), Ni(II), Cu(II), Zn(II). The spectra were all very simple and the principal ions observed in all cases were the molecular anions and ligand ions. Reaction schemes have been established to account for the formation of ligand and other fragment ions, many of which carried less than 0.1% of the total ion currents. Variations in the negative ion mass spectra are attributed to the influence of the metal atom and its 3d electron configuration on the electron capture process. The simplicity of the negative ion mass spectra, together with the fact that many of these metal chelates gave relatively high total ion currents of c. 10^?9–10^?10 A, indicates the potential value of negative ion mass spectrometry in the area of ultra-trace metal analysis, and some estimates of detection limits for some of the metals considered in this study have been made.     

Studies in negative ion mass spectrometry. V—A Comparison of positive a positive and negative ion mass spectra of copper(II) complexes of bidentate schiff base ligands

70 eV positive and negative ion mass spectra of a series of copper(II) Schiff base complexes have been obtained consecutively under the same ion source conditions. The characteristic feature of the negative ion spectra is their extreme simplicity relative to the corresponding positive ion spectra, the only ions present in significant abundance being the molecular anions and ligand ions. The influence of substituents (R) on positive and negative ion fragmentation patterns is discussed. Metastable peaks have been obtained in all cases for the transition [Cu(Ligand)₂]^? → [Ligand]^?.     

Negative ion chemical ionization mass spectra of (η6-arene)Cr(CO)3

The negative ion chemical ionization mass spectra, with ammonia and methane as reagent gases, of the (η⁶-arene)Cr(CO)₃ complexes, where the arene is C₆H₅COCH₃, C₆H₅COC₂H₅, C₆H₅COC₃H₇, C₆H₅COC(CH₃)₃, 2-CH₃C₆H₄COC₃H₇, C₆H₅COOCH₃, C₆H₅CH₃, 1,3,5-(CH₃)₃C₆H₃ and C₆H₅CH₂COC₂H₅, are reported. Similar behaviour is observed with the two reagent gases, but ammonia shows a much higher abundance for the ions produced by reactions of [NH₂]^? with sample molecules. The compounds containing the C₆H₅CO group display an abundant [M]^{? ˙}, whereas the other compounds exhibit [M? H]^? as base peak, produced by ion/molecule reactions. A comparison of the negative ion chemical ionization mass spectra of the (η⁶-arene)Cr(CO)₃ complexes with those of the corresponding ligands shows the strong electron withdrawing power of the Cr(CO)₃ group in the gas phase.     

Electron impact mass spectrometry of diethyl 2-oxysubstituted alkylphosphonates—a remarkably regiospecific α-cleavage

The major electron impact induced fragmentation of 2-hydroxyphosphonic esters, XCH₂CH(OH)CH₂PO₃Et₂ (and their O-derivatives) involves the C(2)–C(3) α-cleavage, yielding the XCH₂^· radical and the oxocarbonium ion, ⁺HO = CHCH₂PO₃Et₂. No evidence for a competitive C(1)–C(2) α-cleavage was obtained, and the results suggest a stabilizing effect of the phosphonyl group on the α-oxocarbonium system.     

η-Pentamethylcyclopentadienylruthenium(II) complexes containing η-coordinated α-amino acids

Reaction of [Cp* RuCl₂]₂ with -alanine ( -alaH) in methanol at room temperature in the presence of NaOMe yields the complex Na[Cp* RuCl( -ala)] (1), which contains a five-membered N,O-coordinated chelate ring. The analogous complex Na[Cp* RuCl( -phe)] (2) is obtained under similar conditions but at 0°C in 90% yield. At temperatures above 20°C both 2 and the η⁶-coordinated complex [Cp* Ru( -pheH)]Cl (4) are obtained, with the proportion of the latter increasing with temperature. Compound 4 is obtained in 88% yield by refluxing [Cp* RuCl₂]₂ and -phenylalanine ( -pheH) in CH₃OH/CH₃ONa followed by separation from 2. The analogous ruthenium(II) sandwich complexes 5–10 were obtained from -tyrosine and -tryptophane and various derivatives. [Cp* Ru( -met)] (3), prepared by the reaction of [Cp* RuCl₂]₂ with -methionine ( -metH) in CH₃OH/CH₃ONa, displays N,O,S-coordination.     

Negative ion mass spectra of a series of fluorinated β-diketones

Electron capture by and the subsequent fragmentation of a series of eleven fluorinated β-diketones of general formula CF₃COCH₂COR has been studied in an MS-50 mass spectrometer. Consecutive loss of two HF molecules from molecular anions occurs with all compounds, as does elimination of CHF₃ from [M ? H]^? ions. Elimination of CO occurs from either \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm M - HF}} \right]_{}^{_.^ - } $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm M - 2HF}} \right]_{}^{_.^ - } $\end{document} ions for five compounds where R ? CF₃ or a cyclic substituent. Kinetic energy release in metastable transitions associated with these HF and CO eliminations has been measured. Intensities of various fragment ions are in part influenced by the ion source temperature. Interaction of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm O}} \right]_{}^{_.^ - } $\end{document} reagent ions with five of the β-diketones under chemical ionization conditions gave [M ? H]^? ions as the only significant ion-molecule reaction product.     

Organometallic chemistry of fullerenes: η2- and η5-(π)complexes

The reactivity of the fullerenes is primarily a function of their strain, as measured by the pyramidalization angle or curvature of the conjugated carbon atoms. A consideration of the orientation of the π-orbitals shows that η²-complexation reactions lead to reaction products with the fullerenes that are very similar to those obtained from unstrained alkenes. Furthermore, a large amount of strain energy is released in this reaction, so it is clear just why this reaction is important in fullerene chemistry. On the other hand, it is shown that the π-orbitals of C₆₀ are poorly oriented for overlap with an exohedral metal atom centered over the five- or six-membered rings, but well disposed for overlap with an endohedral metal atom centered under the five- or six-membered rings. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 139–143, 1998