Darstellung und Charakterisierung der Fulleren-Kokristallisate C60 · 12 C6H12, C70 · 12 C6H12, C60 · 12 CCl4, C60 · 2 CHBr3, C60 · 2 CHCl3, C60 · 2 H2CCl2

Synthesis and Characterization of the Fullerene Co-Crystals C₆₀ · 12 C₆H₁₂, C₇₀ · 12 C₆H₁₂, C₆₀ · 12 CCl₄, C₆₀ · 2CHBr₃, C₆₀ · 2CHCl₃, C₆₀ · 2H₂CCl₂ By crystallization of fullerenes from non-polar solvents (C₆H₁₂, CCl₄, CHBr₃, CHCl₃, H₂CCl₂) compounds of the following compositions were obtained: C₆₀ · 12C₆H₁₂, C₇₀ · 12C₆H₁₂, C₆₀ · 12CCl₄, C₆₀ · 2CHCl₃, C₆₀ · 2CHBr₃ and C₆₀ · 2H₂CCl₂. Lattice parameters have been determined by X-ray diffraction of powder samples; according to single-crystal examinations on C₆₀ · 12C₆H₁₂, C₆₀ · 12CCl₄ and C₆₀ · 2CHBr₃ the fullerene is orientationally disordered. C₆₀ · 12C₆H₁₂, cubic, a = 28.167(1) Å; C₇₀ · 12C₆H₁₂, cubic, a = 28.608(2) Å; C₆₀ · 12CCl₄, cubic, a = 27.42(1) Å; C₆₀ · 2CHBr₃, hexagonal, a = 10.212(1), c = 10.209(1) Å; C₆₀ · 2CHCl₃, hexagonal, a = 10.08(1), c = 10.11(2) Å; C₆₀ · 2H₂CCl₂, tetragonal, a = 16.400(1) Å, c = 11.645(7) Å.     

[C6H6, C3H7 +]and [C6H7 +, C3H6] ion-neutral complexes intermediate in the reactions of protonated propylbenzenes

From the mass-analysed ion kinetic energy spectra of labelled ions, kinetic energy releases and thermodynamic data, it is proved that protonated n-propylbenzene (1) isomerizes into protonated isopropyl benzene (2). It is also shown that the dissociation of the less energetic metastable ions of (2), leading to [iso-C₃H₇]⁺ and [C₆H₇]⁺ product ions, is preceded by H exchange. This H exchange involves two interconverting ion-neutral complexes [C₆H₆, iso-C₃H₇⁺] (2π) and [C₆H₇⁺, C₃H₆] (2α).     

Carbon—carbon formation at a diiron centre by intramolecular coupling of ethoxycarbyne and 1,2-diphenylethenyl ligands in Fe2(CO)6(μ-COC2H5)(μ-C(C6H5)C(C6H5)H). X-ray crystal structure of hexacarbonyl-μ-(1η2,2-diphenyl- 3-ethoxy-η3η1-allyl)-diiron

[Fe₂(CO)₆(μ-CO)(μ-C(C₆H₅)C(C₆H₅)H)]^? reacts with triethyloxonium tetrafluoroborate to yield Fe₂(CO)₆(μ-COC₂H₅)(μ-C(C₆H₅)C(C₆H₅)H). This compound is smoothly transformed at room temperature or more quickly in refluxing hexane into the title compound resulting from the coupling of the ethoxycarbyne and 1,2-diphenylethenyl bridges.     

Investigation of performances of commercial diesel oxidation catalysts for CO,C3H6, and NO oxidation

Four commercial monolithic diesel oxidation catalysts (DOCs) with two different platinum group metal (PGM) loadings and Pt:Pd ratios of 1:0, 2:1, 3:1 (w/w) were investigated systematically for CO, C₃H₆, and NO oxidation, CO-C₃H₆ co-oxidation, and CO-C₃H₆-NO oxidation reactions via transient activity measurements in a simulated diesel engine exhaust environment. As PGM loading increased, light-off curves shifted to lower temperatures for individual and co-oxidation reactions of CO and C₃H₆. CO and C₃H₆ were observed to inhibit theoxidation of themselves and each other. Addition of Pd to Pt was found to enhance CO and C₃H₆ oxidation performance of the catalysts while the presence and amount of Pd was found to increase the extent of self-inhibition of NO oxidation. NO inhibited CO and C₃H₆ oxidation reactions while NO oxidation performance was enhanced in the presence of CO and C₃H₆ probably due to the occurrence of reduced Pt and Pd sites during CO and C₃H₆ oxidations. The optimum Pt:Pd ratio for individual and co-oxidations of CO, C₃H₆, and NO was found to be Pt:Pd = 3:1 (w/w) in the range of experimental conditions investigated in this study.     

The Solitary Isomer of C60H18 Is Proven to Have a C3v Crown Shape: Crystal Structure Determination and Synthesis of Its Triruthenium Cluster Complex

Analytically pure C₆₀H₁₈ is obtained by a Ru₃ cluster complexation and decomplexation method. The crystal structure of C₆₀H₁₈ consists of one flattened hemisphere, to which all 18 hydrogen atoms are symmetrically bonded, and one curved hemisphere akin to C₆₀. A benzenoid ring in the flattened hemisphere is isolated from the residual π systems by a belt composed of sp³‐hybridized CH units. The average out‐of‐plane distances for carbon atoms attached to the benzenoid ring (0.14 Å) is substantially larger than that found in C₆₀F₁₈ (0.06 Å). Several long C(sp³)?C(sp³) single bond lengths [1.61(3)–1.65(3) Å] are observed for C₆₀H₁₈. The reaction of [Ru₃(CO)₁₂] and C₆₀H₁₈ produces [Ru₃(CO)₉(μ₃‐η²,η²,η²‐C₆₀H₁₈)] ( 1 ), where the Ru₃ triangle is regiospecifically linked to the hexagon opposite to the benzenoid ring. Compound 1 is the first transition metal complex of a polyhydrofullerene (fullerane). C₆₀H₁₈ and 1 have been characterized by ¹H and ¹³C NMR, UV/Vis, and mass spectroscopies. The HOMO–LUMO gap of C₆₀H₁₈ is evaluated to be 1.51 V by cyclic voltammetry.     

Reaction of Os3H2(CO)9(C6H4) with diphenylacetylene: the formation and structural characterisation of Os3(CO)7(C6H4)[PhCC(H)Ph]2

The reaction of the 'benzyne' cluster Os₃H₂(CO)₉(C₆H₄) with diphenylacetylene affords the new compound Os₃(CO)₇(C₆H₄)[PhCC(H)Ph]₂; a single crystal X-ray analysis of this product shows that two PhCC(H)Ph units and the benzyne moiety are bonded to the Os₃ core as separate ligands, and that under these conditions there is no ligand condensation.     

Imide and anhydride bridged organoiron dinuclear homo and hetero dichalcogeno carboxylate complexes [CpFe(CO)2ECO(C6H4)CO]2NH and [CpFe(CO)2ECO(C6H4)CO]2O; E = S,Se

Organoiron thio- and seleno-terephthaloyl chloride complexes CpFe(CO)₂ECO(C₆H₄)COCl (E = S and Se) react with NaOH and NaNH₂ to give quantitative yields of the acid Cp(CO)₂ECO(C₆H₄)CO₂H and the amide CpFe(CO)₂ECO(C₆H₄)CONH₂ respectively. These amide and acid derivatives react with the terephthaloyl chloride complexes to give a new series of imide-bridged [CpFe(CO)₂ECO(C₆H₄)CO]₂NH and anhydride-bridged [CpFe(CO)₂ECO(C₆H₄)CO]₂O organoiron dinuclear homo and hetero dichalcogeno terephthalate complexes. The complexes were characterized by elemental analysis, i.r. and ¹H-n.m.r. spectra. This revised version was published online in June 2006 with corrections to the Cover Date.     

Redox-induced hydrogen transfer from hydrofullerene C60H36 to fullerene C60

The possibility of hydrogen transfer from hydrofullerene C₆₀H₃₆ to electrogenerated radical anion C₆₀ ^.− or dianion C₆₀ ²⁻ in propylene carbonate-toluence (3∶2, v/v) was demonstrated by cyclic voltammetry. The process affords C₆₀H₂ as the product. The reaction found is the typical redox-induced process. Translated fromIzvestiya Akodemii Nauk. Seriya Khimicheskaya, No. 6, pp. 1136–1139, June, 1998.     

Radical functionalization of [60]fullerene and its derivatives initiated by the C(CF3)2C6H4F radical

It was found that the 2-(p-fluorophenyl)hexafluoroisopropyl radical produced by thermal dissociation of the Polishchuk dimer [C(CF₃)₂C₆H₄F]₂ can withdraw, under mild conditions, the H atom from the methyl group of toluene and mesitylene to form the corresponding radicals, whose addition to [60]fullerene occurs more selectively than in the case of photochemical production of these radicals. Dynamics of the step-by-step multiaddition of the radicals to C₆₀ was studied by ESR. It was found that the addition of benzyl radicals affords adducts containing from 3 to 5 benzyl groups, whereas no spin-adducts with five addends were observed for more bulky 3,5-dimethylphenylmethyl radicals. The interaction of 3,5-dimethylphenylmethyl radicals with the metal complexes (η²-C₆₀[IrH(CO)(PPh₃)₂] and (η²-C₆₀[Pd(PPh₃)₂] was studied for the first time. It was shown that the palladium derivative undergoes only demetallation. In the case of the Ir complex, up to 3 radicals add to the fullerene ligand in the same hemisphere where the transition metal is coordinated. The reaction rates are ∼5 times lower than those for C₆₀. The ability of 2-(p-fluorophenyl)hexafluoroisopropyl radicals to dehydrogenate C₆₀H₃₆ was found. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1119–1123, June, 1999.     

Benzene carbon-hydrogen bond activation using Ru(C6Me6)[PH(C6H11(2]H2

The dihydride Ru(C₆Me₆)[PH(C₆H₁₁)₂]H₂ is synthesized in high yield by reducing Ru(C₆Me₆)[PH(C₆H₁₁)₂]Cl₂ with Na[AlH₂(OCH₂CH₂OMe)₂]. In benzene it loses hydrogen under UV irradiation to give Ru(C₆Me₆)[PH(C₆H₁₁(₂]H(C₆H₅).     

Measurement of barriers to aryl rotation in Cp(CO)2FeCHC6H5+ and Cp(CO)2FeCH(p-CH3C6H4)+

The first observation of barriers to rotation about the C_arylC_carbene bonds in aryl-substituted metal carbene complexes is reported. Using variable temperature ¹H NMR, barriers of 9.1 and 10.4 kcal/mol have been determined for Cp(CO)₂FeCHC₆H₅⁺ and Cp(CO)₂FeCH(p-CH₃C₆H₄)⁺, respectively. The data clearly indicate a geometry of the complex in which the aryl ring lies coplanar with FeC_carbeneC_ipso plane.     

Darstellung von Tetracarbonyl-triphenylphosphinmanganorganoplumbanen R4−nPb[Mn(CO)4P(C6H5)3]n (RCH3, C6H5; n = 1,2)

Preparation of R_4?nPb[Mn(CO)₄P(C₆H₅)₃]_n Compounds (R?CH₃, C₆H₅; n = 1, 2) As the first examples of organolead manganese carbonyls substituted in the manganese carbonyl ligand compounds of the type R_4?nPb[Mn(CO)₄P(C₆H₅)₃]_n (R?CH₃, C₆H₅; n = 1, 2) have been prepared by the alkali salt method from R_4?nPbCl_n and NaMn(CO)₄P(C₆H₅)₃. (C₆H₅)₂Sn[Mn(CO)₄P(C₆H₅)₃]₂ has been gained by the same method and also by thermal ligand exchange. According the IR data the ligand P(C₆H₅)₃ is trans to the tetrahedrally surrounded lead. In solution to compounds are monomeric.     

The 31P NMR spectra of ArCr(CO)2P(C6H5)3 compounds in neutral and acidic media

The ³¹P NMR spectra of C₆H₅XCr(CO)₂P(C₆H₅)₃ (X = H, CH₃, OCH₃, N(CH₃)₂, COOCH₃) (I), p-C₆H₄X₂Cr(CO)₂P(C₆H₅)₃ (X = COOCH₃)(II) and C₆H₃X₃Cr(CO)₂P(C₆H₅)₃ (X = CH₃) (III) complexes in neutral and acidic media were investigated. The protonation of complexes I and III in trifluoroacetic acid results in the greater upfield shielding of ³¹P{¹H} signal. In this case the complexes I (X = H, CH₃, OCH₃) are completely protonated at the metal, complex I (X = COOCH₃)is partially protonated, while no protonation occurs in the case of complex II.Temperature-dependence of the ³¹P{¹H} NMR spectra was investigated for complexes I (X = H, OCH₃) in a 1/10 mixture of trifluoroacetic acid and toluene and for complexes I (X = COOCH₃) and II in trifluoroacetic acid. The degree of protonation was found to increase with decreasing temperature.     

Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H,Me, Ph)

The reactivity of a series of iridium? pyridylidene complexes with the formula [Tp^Me2Ir(C₆H₅)₂(C(CH)₃C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H₂, O₂, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e^? unsaturated [Tp^Me2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H₂ is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO₂, and H₂C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH₂CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH₂)N moiety. C₆H₅(C?O)H and C₆H₅C?CH react with formation of Ir? C₆H₅ and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O₂ is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.     

A tandem mass spectrometry study of the gas phase RSC6H5Cr+L (R = H,C6H5; L = arene) and C6H5SSC6H5Cr+ ions

Ion-molecule reactions of chromium containing ions with arylsulfides have been studied in the gas phase and their products have been characterized by tandem mass spectrometry. C₆H₅SH and (C₆H₅)₂S react as typical aromatic compounds and give rise to Cr⁺C₆H₅SR] and RC₆H₅Cr⁺QH₅SR′ [R = H, CH₃, CH(CH₃)₂; R′ = H, C₆H₅] ions. Metastable ion mass spectra of the latter species show that the metal is more strongly bound to diphenylsulfide than to alkylbenzenes. C₆H₅SSC₆H₅ reacts with chromium-containing ions to form only Cr⁺(C₆H₅SSC₆H₅). The decomposition characteristics of this ion and, in particular, the presence of a recovery signal in the neutralization-reionization mass spectrum are in keeping with the formation of a 1,2-dithia[2]cyclophane complex ion, which rearranges into a structurel(s) that contains Cr?S bond(s). No evidence was found for metal atom insertion into S?S, C?S, or S?H bonds.     

Neue Synthesen und Kristallstrukturen von Bis(fluorphenyl)quecksilber,Hg(Rf)2 (Rf = C6F5, 2, 3, 4, 6‐F4C6H, 2, 3, 5, 6‐F4C6H, 2, 4, 6‐F3C6H2, 2, 6‐F2C6H3)

New Syntheses and Crystal Structures of Bis(fluorophenyl) Mercury, Hg(R_f)₂ (R_f = C₆F₅, 2, 3, 4, 6‐F₄C₆H, 2, 3, 5, 6‐F₄C₆H, 2, 4, 6‐F₃C₆H₂, 2, 6‐F₂C₆H₃) Bis(fluorophenyl) mercury compounds, Hg(R_f)₂ (R_f = C₆F₅, C₆HF₄, C₆H₂F₃, C₆H₃F₂), are prepared in good yields by the reactions of HgF₂ with Me₃SiR_f. The crystal structures of Hg(2, 3, 4, 6‐F₄C₆H)₂ (monoclinic, P2₁/n), Hg(2, 3, 5, 6‐F₄C₆H)₂ (monoclinic, C2/m), Hg(2, 4, 6‐F₃C₆H₂)₂ (monoclinic, P2₁/c) and Hg(2, 6‐F₂C₆H₃)₂ (triclinic, P1) are described.     

Chemical ionization mass spectra of selected C3H6O compounds

The chemical ionization mass spectra of five isomers of C₃H₆O (acetone, propionaldehyde, oxetane, propylene oxide and allyl alcohol) have been determined using a variety of reagent gases (H₂, D₂, N₂/H₂, CO₂/H₂ and CO/H₂). The [C₃H₇O]⁺ ions produced by protonation of these isomers undergo very similar reactions to those reported for analogous [C₃H₇O]⁺ metastable ions; however, decomposing ions generated by chemical ionization appear to have somewhat higher internal energies. The results of ²H labelling studies (D₂ reagent gas or labelled analogues of C₃H₆O) indicate that protonation occurs mainly on oxygen and are consistent with previous investigations of metastable oxonium ions. The protonated acetone ion is particularly stable, in agreement with the higher activation energies for fragmentation of this isomer than for other [C₃H₇O]⁺ structures. As the calculated heat of protonation of C₃H₆O is reduced by changing the reagent gas, so the extent to which fragmentation occurs decreases. This is discussed in the context of competition between fragmentation and collisional stabilization of the excited [C₃H₇O]⁺* ion. It is concluded that on average a large fraction (approaching 1) of the exothermicity of the protonation reaction resides in the [C₃H₇O]⁺* ions produced initially.     

Scalable Green Synthesis of Robust Ultra-Microporous Hofmann Clathrate Material with Record C3H6 Storage Density for Efficient C3H6/C3H8 Separation

Developing porous materials for C₃H₆/C₃H₈ separation faces the challenge of merging excellent separation performance with high stability and easy scalability of synthesis. Herein, we report a robust Hofmann clathrate material (ZJU-75a), featuring high-density strong binding sites to achieve all the above requirements. ZJU-75a adsorbs large amount of C₃H₆ with a record high storage density of 0.818 g mL⁻¹, and concurrently shows high C₃H₆/C₃H₈ selectivity (54.2) at 296 K and 1 bar. Single-crystal structure analysis unveil that the high-density binding sites in ZJU-75a not only provide much stronger interactions with C₃H₆ but also enable the dense packing of C₃H₆. Breakthrough experiments on gas mixtures afford both high separation factor of 14.7 and large C₃H₆ uptake (2.79 mmol g⁻¹). This material is highly stable and can be easily produced at kilogram-scale using a green synthesis method, making it as a benchmark material to address major challenges for industrial C₃H₆/C₃H₈ separation.     

Transition-metal mediated heteroatom removal by reactions of FeL+ [L=O,C4H6, c-C5H6, c-C5H5, C6H6, C5H4(=CH2)] with furan,thiophene, and pyrrole in the gas phase

Reactions of Fe⁺ and FeL⁺ [L=O, C₄H₆, c-C₅H₆, C₅H₅, C₆H₆, C₅H₄(=CH₂)] with thiophene, furan, and pyrrole in the gas phase by using Fourier transform mass spectrometry are described. Fe⁺, Fe(C₅H₅)⁺, and FeC₆H ₆ ⁺ yield exclusive rapid adduct formation with thiophene, furan, and pyrrole. In addition, the iron-diene complexes [FeC₄H ₆ ⁺ and Fe(c-C₅H₆)⁺], as well as FeC₅H₄(=CH₂)⁺ and FeO⁺, are quite reactive. The most intriguing reaction is the predominant direct extrusion of CO from furan by FeC₄H₆ ⁺, Fe(c-C₅H₆)⁺, and FeC₅H₄(=CH₂)⁺. In addition, FeC₄H ₆ ⁺ and Fe(c-C₅H₆)⁺ cause minor amounts of HCN extrusion from pyrrole. Mechanisms are presented for these CO and HCN extrusion reactions. The absence of CS elimination from thiophene may be due to the higher energy requirements than those for CO extrusion from furan or HCN extrusion from pyrrole. The dominant reaction channel for reaction of Fe(c-C₅H₆)⁺ with pyrrole and thiophene is hydrogen-atom displacement, which implies D^O(Fa(N₅H₅)⁺-C₄H₄X)>D^O(Fe(C₅H₅)⁺-H)=46±5 kcal mol^?1. D^O(Fe⁺-C₄H₄S) and D^O(Fe⁺-C₄H₅N)=D^O(Fe⁺-C₄H₆)=48±5 kcal mol^?1. Finally, 55±5 kcal mol^?1=D^O(Fe⁺-C₆H₆)>D^O(Fe⁺-C₄H₄O)>D^O(Fe⁺-C₂H₄)=39.9±1.4 kcal mol^?1. FeO⁺ reacts rapidly with thiophene, furan, and pyrrole to yield initial loss of CO followed by additional neutral losses. D^O(Fe⁺-CS)>D^O(Fe⁺-C₄H₄S)≈48±5 kcal mol^?1 and D^O(Fe⁺-C₄H₅N)≈48±5 kcal mol^?1>D^O(Fe⁺-HCN)>D^O(Fe⁺-C₂H₄)=39.9±1.4 kcal mil^?1.     

Reaction of (η5‐C5H5)Fe(CO)2I with Anionic Bidentate Phosphine Ligands PPh2(o‐C6H4NHLi) or PPh2(o‐C6H4OLi)

The o‐substituted hybrid phenylphosphines, PPh₂(o‐C₆H₄NH₂) and PPh₂(o‐C₆H₄OH), could be deprotonated with LDA or n‐BuLi to yield PPh₂(o‐C₆H₄NHLi) and PPh₂(o‐C₆H₄OLi), respectively. When added to a solution of (η⁵‐C₅H₅)Fe(CO)₂I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η⁵‐C₅H₅)Fe(CO)[C(O)NH(o‐C₆H₄)PPh₂‐C,P‐η²] for the former and mainly a zwitterionic complex 2 , (η⁵‐C₅H₅)Fe⁺(CO)₂[PPh₂(o‐C₆H₄O^?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η⁵‐C₅H₅)Fe(CO){NH₂(o‐C₆H₄)PPh₂‐N,P‐η²}⁺]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.