Unimolecular reactions of the isolated immonium ions CH3CH = NH+C4H9, CH3CH2Ch = NH+C4H9 and (CH3)2C = NH+C4H9

The reactions of ten metastable immonium ions of general structure R¹R²C?NH⁺C₄H₉ (R¹ = H, R² = CH₃, C₂H₅; R¹ = R² = CH₃) are reported and discussed. Elimination of C₄H₈ is usually the dominant fragmentation pathway. This process gives rise to a Gaussian metastable peak; it is interpreted in terms of a mechanism involving ion-neutral complexes containing incipient butyl) cations. Metastable immonium ions ontaining an isobutyl group are unique in undergoing a minor amount of imine (R¹R²C?NH) loss. This decomposition route, which also produces a Gaussian metastable peak, decreases in importance as the basicity of the imine increases. The correlation between imine loss and the presence of an isobutyl group is rationalized by the rearrangement of the appropriate ion-neutral complexes in which there are isobutyl cations to the isomeric complexes containing the thermodynamically more stable tert-butyl cations. A sizeable amount of a third reaction, expulsion of C₃H₆, is observed for metastable n-C₄H₉ ⁺NH?CR¹R² ions; in contrast to C₄H₈ and R¹R²C?NH loss, C₃H₆ elimination occurs with a large kinetic energy release (40–48 kJ mol^?1) and is evidenced by a dish-topped metastable peak. This process is explained using a two-step mechanism involving a 1,5-hydride shift, followed by cleavage of the resultant secondary open-chain cations, CH₃CH⁺ CH₂CH₂NHCHR¹R².     

Copper(II) and Nickel(II) Alkylxanthate Complexes (R = C2H5, i-C3H7, i-C4H9, s-C4H9, and C5H11): EPR and Solid-State 13C CP/MAS NMR Studies

Alkylxanthate complexes of the general formula [M{S(S)COR}₂] (M = Ni, ⁶³Cu, and ⁶⁵Cu; R = C₂H₅, i-C₃H₇, i-C₄H₉, s-C₄H₉, and C₅H₁₁) were synthesized and studied by EPR and high-resolution solid-state ¹³C CP/MAS NMR. In the copper(II) complexes stabilized in the matrix of nickel(II) compounds, square planar chromophores [CuS₄] are characterized by rhombic distortion (EPR data). Experimental EPR spectra were simulated at the second order of perturbation theory. Nickel(II) complexes were characterized by ¹³C NMR spectra. In all cases, the –OC(S)S– groups were found to exhibit intramolecular structural equivalence.     

ESR and solid-state natural abundance 13C CP/MAS NMR study of crystalline alkyl (R = C2H5, i-C3H7, i-C4H9, s-C4H9, and C5H11) xanthate copper(II) and thallium(I) complexes

Crystalline thallium(I) alkylxanthate complexes [Tl{S(S)COR}]_n (R = C₂H₅, i-C₃H₇, i-C₄H₉, s-C₄H₉, and C₅H₁₁) and isotope-substituted heteropolynuclear Cu(II)Tl(I) complexes [⁶³⁽⁶⁵⁾CuTl₆(S₂COR)₈] (R= i-C₄H₉ and C₅H₁₁) were obtained and studied by ESR and high-resolution solid-state ¹³C CP/MAS NMR spectroscopy. According to the ¹³C NMR data, polynuclear thallium(I) complexes contain structurally equivalent alkylxanthate ligands. The ESR study revealed the Jahn-Teller dynamic effect in Cu(II)Tl(I) complexes; the nuclei of six Tl atoms are involved in the hyperfine interaction.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 48–54.Original Russian Text Copyright © 2005 by Ivanov, Bredyuk, Antzutkin, Forsling.     

(C_5H_9C_5H_4)_3NdBrLi(THF)_3和(C_5H_9C_5H_4)_3SmTHF的合成与结构

无水三氯化钕与环戊烷基环戊二烯钠、溴化锂(1:2:1摩尔比)反应,除去不溶物和溶剂后,产物在己烷/四氢呋喃溶剂中冷冻得到兰紫色晶体(C5H9C5H4)3NdBrLi(THF)3(配合物1)。其中心金属Nd3+的配位数为10,以η5与3个环戊二烯基相连,并通过单溴原子桥连锂原子,形成双核结构。该晶体属三斜晶系,P`1空间群。晶体学参数为a=12.048(2)、b=13.498(3)、c=13.831(3);α=104.16(3)、β=104.07(3)、γ=95.96(3); V=2083.3(7)3、Z=2、Dc=1.35Mg/m3、Mr=847.01gmol-1、F(000)=874。无水三氯化钐与环戊烷基环戊二烯钠(1:3)反应,产物在-30oC下的己烷溶剂中结晶得桔红色晶体(C5H9C5H4)3SmTHF(配合物2)。该晶体属正交晶系,Fdd2空间群。晶胞参数a=28.175(5) 、b=46.24(2)、c=9.167(4);V=11943(8)3、Z=16、Dc=1.38Mg/m3、 Mr=622.11 g·mol-1、F(000)=5136。10配位的金属Sm3+与3个环戊二烯基以η5相连,并结合一个四氢呋喃溶剂分子。     

Comparative study of the hypercoordinate ions C7H9+ and C8H9+ by the ab initio/GIAO-CCSD(T) method

A comparative study of the hypercoordinate square-pyramidal carbocations C7H9+ and C8H9+ was performed by the ab initio/GIAO-CCSD(T) method. The structures and 13C NMR chemical shifts of the cations were calculated at the GIAO-CCSD(T)/tzp/dz//MP2/cc-pVTZ level. The bishomo square pyramidal structure 1 was calculated for C7H9+ at the MP2/cc-pVTZ level. The calculated 13C NMR chemical shifts of structure 1 agree extremely well with the experimental values. However, unlike for C7H9+ both the bishomo square pyramidal structure 3 and the trishomocyclopropenium type structure 4 were found to be minima on the potential energy surface of C8H9+. They are very close energetically with cation 3, only 0.7 kcal/mol less stable than cation 4 at the MP2/cc-pVTZ//MP2/cc-pVTZ + ZPE level. Neither structure 3 nor 4 yields NMR spectra that agree with experiment. However, a weighted average of the two reproduces the observed NMR spectrum of C8H9+ (at -80 degrees C) quite well.     

Electrosynthesis of Rh2(dpf)4(R) where dpf = N,N'-diphenylformamidinate anion and R = CH3, C2H5, C3H7, C4H9 or C5H11

The electrosynthesis of Rh(2)(dpf)(4)(R) where dpf is the N,N'-diphenylformamidinate anion and R = CH(3), C(2)H(5), C(3)H(7), C(4)H(9) or C(5)H(11) was carried out in THF containing 0.2 M tetra-n-butylammonium perchlorate (TBAP) and one of several alkyl iodides represented as RI. The initial step in the reaction involved a one-electron reduction of the Rh(2)(4+) unit in Rh(2)(dpf)(4) to its Rh(2)(3+) form followed by a homogeneous reaction involving electrogenerated [Rh(2)(dpf)(4)](-) and the alkyl iodide in solution to give Rh(2)(dpf)(4)(R). The homogeneously generated Rh(2)(5+) product was then immediately reduced by a second electron at the potential where [Rh(2)(dpf)(4)(R)](-) is generated, giving [Rh(2)(dpf)(4)(R)](-) which contains a Rh(2)(4+) center as a final product of an electrochemical ECE mechanism. The electrosynthesized [Rh(2)(dpf)(4)(CH(3))](-) derivative could be reoxidized to Rh(2)(dpf)(4)(CH(3)) on the reverse potential sweep and both forms of the CH(3) bonded derivative were in situ characterized by cyclic voltammetry combined with UV-visible and/or ESR spectroscopy. The reversible Rh(2)(4+/3+) process of Rh(2)(dpf)(4) is located at E(1/2) = -1.11 V in THF, 0.2 M TBAP while the electrogenerated Rh(2)(dpf)(4)(R) products are substantially easier to reduce, with E(p) values for the Rh(2)(5+/4+) couples ranging from -0.50 to -0.54 V vs. SCE depending upon the specific R group.     

Ab initio/GIAO-CCSD(T) study of structures, energies, and 13C NMR chemical shifts of C4H7(+) and C5H9(+) ions: relative stability and dynamic aspects of the cyclopropylcarbinyl vs bicyclobutonium ions

The structures and energies of the carbocations C 4H 7 (+) and C 5H 9 (+) were calculated using the ab initio method. The (13)C NMR chemical shifts of the carbocations were calculated using the GIAO-CCSD(T) method. The pisigma-delocalized bisected cyclopropylcarbinyl cation, 1 and nonclassical bicyclobutonium ion, 2 were found to be the minima for C 4H 7 (+) at the MP2/cc-pVTZ level. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level the structure 2 is 0.4 kcal/mol more stable than the structure 1. The (13)C NMR chemical shifts of 1 and 2 were calculated by the GIAO-CCSD(T) method. Based on relative energies and (13)C NMR chemical shift calculations, an equilibrium involving the 1 and 2 in superacid solutions is most likely responsible for the experimentally observed (13)C NMR chemical shifts, with the latter as the predominant equilibrating species. The alpha-methylcyclopropylcarbinyl cation, 4, and nonclassical bicyclobutonium ion, 5, were found to be the minima for C 5H 9 (+) at the MP2/cc-pVTZ level. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level ion 5 is 5.9 kcal/mol more stable than the structure 4. The calculated (13)C NMR chemical shifts of 5 agree rather well with the experimental values of C 5H 9 (+).     

Probing isomeric differences of phosphorylated carbohydrates through the use of ion/molecule reactions and FT-ICR MS

Through the use of ion/molecule reactions and tandem mass spectrometry, phosphate position is assigned in both phosphorylated monosaccharides and oligosaccharides. In previous work phosphate moieties of monosaccharides were stabilized under collisional activation, by first derivatizing the deprotonated monosaccharide with trimethyl borate through an ion/molecule reaction, and the phosphate position determined through marker ions generated in tandem mass spectra. In this work, the methodology is extended to larger phosphorylated oligomers employing chlorotrimethylsilane (TMSCl) as the ion/molecule reagent. Phosphorylated monosaccharides were first investigated to determine diagnostic ions for phosphate linkage in monomeric standards. It was observed that the diagnostic ions showed both linkage and some monosaccharide stereochemical information. Furthermore, it was observed that TMS addition stabilized the phosphate moiety under collisionally activated conditions. Upon identification of the diagnostic ions, the methodology was applied to lactose-1-phosphate. It was found that TMSCl, stabilized the phosphate moiety upon collisional activation, and furthermore, the phosphate linkage could be determined through tandem mass spectrometric analysis. As a further extrapolation to biologically relevant problems, the methodology was applied to a lipophosphoglycan analog from the protozoan parasite Leishmania. This sample contains bridging phosphates which were converted to terminal phosphates through collision induced dissociation. The sample was then analyzed in the same manner as lactose-1-phosphate, yielding phosphate linkage information and stereochemical information. This study showed that, using the developed methodology, phosphate linkage can be determined from both monosaccharides and larger oligosaccharides; furthermore it is applicable to samples in which the phosphates are either terminating or bridging.     

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.     

Synthesis of new 4(3H)-quinazolinone derivatives using 5(4H)-oxazolones

New derivatives of 5(4H)-quinazolinone containing 2-imidazolin-5-one rings have been prepared from 5(4H)-oxazolone derivatives.     

An investigation of secondary ion yield enhancement using Bi n 2+ (n=1, 3, 5) primary ions

We have investigated secondary ion yield enhancement using Bin2+ (n=1, 3, 5) primary ions impacting phenylalanine, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE), cholesterol, Irganox 1010, and polymer films adsorbed on silicon and aluminum. Secondary ion yields are increased using Bi2+and Bi3(2+) primary ions for the molecular layers and polymers that can undergo allyl cation rearrangements. For Irganox 1010, the deprotonated molecular ion yields (m/z 1175; [M-H]-) are one to two times larger for Bi2+ and Bi(3)2+ primary ions than for Bi+ and Bi3+ at the same primary ion velocities. In the positive ion mode, the largest fragment ion yield (m/z 899) is 1.5 times larger for Bi2+ ions than for Bi+. For Bi3(2+) the largest fragment ion yield is only 70% of the ion yield using Bi3+, but the secondary ion yields of the fragment ions at m/z 57 and 219 are enhanced. For polymers that can undergo allyl cation rearrangement reactions the secondary ion yield enhancements of the monomer ions range from 1.3 to 4.3. For Bi(5)2+ primary ions, secondary ion yields were the same or slightly larger than for Bi5+ in the negative ion mass spectra for Irganox 1010, but lower in the positive ion mode. No secondary ion yield enhancements were measured on polymer samples for Bi5(2+). For all polymer films studied, secondary ion intensities from the oligomer regions are substantially decreased using Bin2+ (n=1, 3, 5). We discuss differences in the ionization mechanisms for doubly and singly-charged Bi primary ion bombardment.     

Arrhenius parameters for the reactions CH3. + C4H10 → CH4 + C4H9. and C2H5. + C4H10 → C2H6 + C4H9.

Study of n-butane pyrolysis at high temperature in a flow system allows measurement of the sum of the rate constants of the initiation reactions and of the Arrhenius parameters of the reactions Established data for k₁/k₂ allow estimation of k₁ for 951°K and this, with recent thermochemical data, yields the result log k_?1 (l.mole s^?1) = 8.5, in remarkable agreement with a recent measurement [20] but over si×ty times smaller than conventional assumption. The product k₃k₄ (l.²mole^?2s^?2) is found to be associated with the Arrhenius parameters log (A₃A₄) = 21.90 ± 0.6 and (E₃ + E₄) = 38.3 ± 2.7 kcal/mole. These values are much higher than would be e×pected on the basis of low temperature estimates. Independent evaluation gives log A₄ = 10.5 ± 0.4 (l.mole^?1s^?1) and E₄ = 20.1 ± 1.7 kcal/mole, hence log A₃ = 11.4 ± 0.8 (l.mole^?1s^?1) and E₃ = 18.2 ± 3.2 kcal/mole. These values are shown to be entirely consistent with a wide range of results from pyrolytic studies, and it is argued that they further confirm the view that Arrhenius plots for alkyl radical–alkane metathetical reactions are strongly curved, in part due to tunneling and, appreciably, to other as yet unidentified effects. Since there is published evidence that metathetical reactions involving hydrogen atoms show even greater curvature, it is suggested that this may be a characteristic of many metathetical reactions.     

Metastable and collision-induced fragmentation studies and thermochemistry of isomeric C(4)H(11)Si(+) ions and their adducts with C(4)H(12)Si silanes

Metastable Ion (MI) and collision-induced dissociation (CID) mass spectra for all isomeric even-electron [C(4)H(12)Si - H](+) ions were recorded and compared. Deuterium labeling experiments indicated that most precursors give rise to silylium ions. Silylium ions with two or more methyl groups are found to lose C(2)H(4) after isomerization via a straightforward hydrogen transfer to the appropriate ethylsilylium ion. Similarly, all isomeric propyl- and butyl-containing silylium ions are found to lose C(2)H(4) by rearrangement preceding dissociation. In the CI source of the mass spectrometer many of the silylium ions are found to cluster with the parent neutral silane present in the source to give stable [M - H](+)+M adduct ions. The MI and CID spectra of these adduct ions were also obtained. In the MI spectra of all adducts, except i-BuSiH(3), only the starting silylium ion is observed. Under CID conditions generation of silylium ions dominates. Deuterium labeling studies show that this dissociation may be accompanied by some rearrangement, in particular for the adducts from i-BuSiH(3). High-pressure mass spectrometric clustering equilibrium measurements were also carried out to determine the enthalpies and entropies of binding of the silylium ions to the neutral silanes. These measurements yield insight into the effects of various alkyl group substitutions on the association thermochemistry in these adducts. Copyright 2000 John Wiley & Sons, Ltd.