Reforming of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Gliding Arc System: Effects of Operational Parameters and Oxygen Addition in Feed

In this research, the reforming of simulated natural gas containing a high CO₂ content under AC non-thermal gliding arc discharge with partial oxidation was conducted at ambient temperature and atmospheric pressure, with specific regards to the concept of the direct utilization of natural gas. This work aimed at investigating the effects of applied voltage and input frequency, as well as the effect of adding oxygen on the reaction performance and discharge stability in the reforming of the simulated natural gas having a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20. The results showed marked increases in both CH₄ conversion and product yield with increasing applied voltage and decreasing input frequency. The selectivities for H₂, C₂H₆, C₂H₄, C₄H₁₀, and CO were observed to be enhanced at a higher applied voltage and at a lower frequency, whereas the selectivity for C₂H₂ showed an opposite trend. The use of oxygen was found to provide a great enhancement of the plasma reforming of the simulated natural gas. For the combined plasma and partial oxidation in the reforming of CO₂-containing natural gas, air was found to be superior to pure oxygen in terms of reactant conversions, product selectivities, and specific energy consumption. The optimum conditions were found to be a hydrocarbons-to-oxygen feed molar ratio of 2/1 using air as an oxygen source, an applied voltage of 17.5 kV, and a frequency of 300 Hz, in providing the highest CH₄ conversion and synthesis gas selectivity, as well as extremely low specific energy consumption. The energy consumption was as low as 2.73 × 10⁻¹⁸ W s (17.02 eV) per molecule of converted reactant and 2.49 × 10⁻¹⁸ W s (16.60 eV) per molecule of produced hydrogen.     

Combined Reforming and Partial Oxidation of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Multistage Gliding Arc Discharge System: Effect of Stage Number of Plasma Reactors

The effect of stage number of multistage AC gliding arc discharge reactors on the process performance of the combined reforming and partial oxidation of simulated CO₂-containing natural gas having a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20 was investigated. For the experiments with partial oxidation, either pure oxygen or air was used as the oxygen source with a fixed hydrocarbon-to-oxygen molar ratio of 2/1. Without partial oxidation at a constant feed flow rate, all conversions of hydrocarbons, except CO₂, greatly increased with increasing number of stages from 1 to 3; but beyond 3 stages, the reactant conversions remained almost unchanged. However, for a constant residence time, only C₃H₈ conversion gradually increased, whereas the conversions of the other reactants remained almost unchanged. The addition of oxygen was found to significantly enhance the process performance of natural gas reforming. The utilization of air as an oxygen source showed a superior process performance to pure oxygen in terms of reactant conversion and desired product selectivity. The optimum energy consumption of 12.05 × 10²⁴ eV per mole of reactants converted and 9.65 × 10²⁴ eV per mole of hydrogen produced was obtained using air as an oxygen source and 3 stages of plasma reactors at a constant residence time of 4.38 s.     

Natural gas permeation in polyimide membranes

Polyimide membranes derived from 6FDA-DAM:DABA and 6FDA-6FpDA:DABA copolymers have been used to separate 50/50 CO₂/CH₄ mixtures and multicomponent synthetic natural gas mixtures at 35 °C and feed pressures up to 55 atm. For 6FDA-DAM:DABA 2:1 membranes the effects of thermal annealing and covalent crosslinking are decoupled with respect to effects on permeabilities and selectivity. Crosslinking at 295 °C with 1,4-butylene glycol and 1,4-cyclohexanedimethanol increases CO₂ permeabilities by factors of 4.1 and 2.4, respectively, at 20 atm feed pressure, without a loss in selectivity, relative to crosslinking at 220 °C. Thermal annealing and crosslinking also reduce CO₂ plasticization effects. Crosslinking of DABA-containing copolymers, therefore, can produce membranes with tunable transport properties that offer significantly higher performance with better plasticization-resistance than that reported in the literature for the commercial polymers Matrimid^® and cellulose acetate for CO₂ removal from natural gas mixtures. Separation of complex mixtures containing CO₂, CH₄, C₂H₆, C₃H₈, and C₄H₁₀ or toluene results in a significant decrease of the CO₂ permeability, but only a moderate decrease in the CO₂/CH₄ selectivity.     

Adsorption of natural gas and its whole components on adsorbents

Adsorption of each component of natural gas on adsorbent prepared from petroleum coke was studied. At 25 °C and 3.5 MPa, adsorption capacity of the components of natural gas are as follows: C₃H₈, H₂S(0.980) > CO₂(0.691) > C₂H₆(0.160) > CH₄(0.136) > N₂(0.096) (g/g). For natural gas, adsorption capacity is 145.2 (mL/mL) and delivery capacity is 105.7 (mL/mL). One equation between adsorption capacity and boiling point of adsorbed gas was firstly generalized. The adsorption capacity of different component like O₂, N₂, CH₄, C₂H₆, CO₂, H₂S on adsorbents were predicted using the equation. The results fit well with the experimental data. The equation has significance in predicting the adsorption capacity for any component of natural gas. Charge-discharge tests were conducted 10 times, the result indicates that natural gas has significantly worse reversibility in adsorption and desorption in the adsorbent than that of CH₄. The contents of the components after 10 charge-discharge show that the adsorption capacity drop of natural gas is due to the irreversible adsorption of heavy or polar components like C₃H₈, H₂S.     

Steric effects on the singlet-triplet energy gaps of five-membered ring R<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>2</Subscript>M

Thermal internal energy gaps, ΔE _s−t; enthalpy gaps, ΔH _s−t; Gibbs free energy gaps, ΔD _s−t, between singlet (s) and triplet (t) states of R₂C₄H₂M (M = C, Si, and Ge) were calculated at B3LYP/6-311++G** level of theory. The ΔG _s−t of R₂C₄H₂C was increased in the order (in kcal/mol): R = −CH₃ (−10.51) > −H (−9.59) > i-Pr (−9.51) > t-Bu (−8.98). While, the ΔG _s−t of R₂C₄H₂Si and R₂C₄H₂Ge were increased in the order (in kcal/mol): −CH₃ (17.01) > i-Pr (15.30) > −H (15.26) > t-Bu (14.35) and -H (22.79) > −CH₃ (22.69) > i-Pr (21.66) > t-Bu (21.01), respectively.     

A Microporous Metal‐Organic Framework Supramolecularly Assembled from a CuII Dodecaborate Cluster Complex for Selective Gas Separation

A novel 3D metal‐organic framework BSF‐1 based on the closo‐dodecaborate cluster [B₁₂H₁₂]^2? was readily prepared at room temperature by supramolecular assembly of CuB₁₂H₁₂ and 1,2‐bis(4‐pyridyl)acetylene. The permanent microporous structure was studied by X‐ray crystallography, powder X‐ray diffraction, IR spectroscopy, thermogravimetric analysis, and gas sorption. The experimental and theoretical study of the gas sorption behavior of BSF‐1 for N₂, C₂H₂, C₂H₄, CO₂, C₃H₈, C₂H₆, and CH₄ indicated excellent separation selectivities for C₃H₈/CH₄, C₂H₆/CH₄, and C₂H₂/CH₄ as well as moderately high separation selectivities for C₂H₂/C₂H₄, C₂H₂/CO₂, and CO₂/CH₄. Moreover, the practical separation performance of C₃H₈/CH₄ and C₂H₆/CH₄ was confirmed by dynamic breakthrough experiments. The good cyclability and high water/thermal stability render it suitable for real industrial applications.     

Identifying Optimal Zeolitic Sorbents for Sweetening of Highly Sour Natural Gas

Raw natural gas is a complex mixture comprising methane, ethane, other hydrocarbons, hydrogen sulfide, carbon dioxide, nitrogen, and water. For sour gas fields, selective and energy‐efficient removal of H₂S is one of the crucial challenges facing the natural‐gas industry. Separation using nanoporous materials, such as zeolites, can be an alternative to energy‐intensive amine‐based absorption processes. Herein, the adsorption of binary H₂S/CH₄ and H₂S/C₂H₆ mixtures in the all‐silica forms of 386 zeolitic frameworks is investigated using Monte Carlo simulations. Adsorption of a five‐component mixture is utilized to evaluate the performance of the 16 most promising materials under close‐to‐real conditions. It is found that depending on the fractions of CH₄, C₂H₆, and CO₂, different sorbents allow for optimal H₂S removal and hydrocarbon recovery.     

Oberflächenverbindungen von Übergangsmetallen. XXX. Fischer-Tropsch-analoge Umsetzung von CO/H2 bzw. CO2/H2 an Oberflächen-Chrom(II)

Surface Compounds of Transition Metals. XXX. Fischer-Tropsch Analogous Reactions of CO/H₂ and CO₂/H₂ on Surface Chromium(II) Surface chromium(II)/silicagel catalyzes the reduction of CO and CO₂ by hydrogen to CH₄, C₂H₆ and C₃H₈. The catalyst is partially desactivated by this reaction, but a permanent activity of ca. 30% remains. – The reaction can be formulated via the sequence formaldehyde complex → <CH₂>-complex → alkane. If cycloalkenes or chlorobenzene are added simultaneously, these scavenger molecules are methylated by <CH₂>.     

Gas sorption and characterization of poly(ether‐b‐amide) segmented block copolymers

The solubilities of He, H₂, N₂, O₂, CO₂, CH₄, C₂H₆, C₃H₈, and n‐C₄H₁₀ were determined at 35°C and pressures up to 27 atmospheres in a systematic series of phase separated polyether–polyamide segmented block copolymers containing either poly(ethylene oxide) [PEO] or poly(tetramethylene oxide) [PTMEO] as the rubbery polyether phase and nylon 6 [PA6] or nylon 12 [PA12] as the hard polyamide phase. Sorption isotherms are linear for the least soluble gases (He, H₂, N₂, O₂, and CH₄), convex to the pressure axis for more soluble penetrants (CO₂, C₃H₈, and n‐C₄H₁₀) and slightly concave to the pressure axis for ethane. These polymers exhibit high CO₂/N₂ and CO₂/H₂ solubility selectivity. This property appears to derive mainly from high carbon dioxide solubility, which is ascribed to the strong affinity of the polar ether linkages for CO₂. As the amount of the polyether phase in the copolymers increases, gas solubility increases. The solubility of all gases is higher in polymers with less polar constituents, PTMEO and PA12, than in polymers with more polar PEO and PA6 units. CO₂/N₂ and CO₂/H₂ solubility selectivity, however, are higher in polymers with higher concentrations of polar repeat units. The sorption data are complemented with physical characterization (differential scanning calorimetry, elemental analysis, and wide angle X‐ray diffraction) of the various block copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2463–2475, 1999     

Adsorption equilibria of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> in cation-exchanged zeolites 13X

Ion-exchange with different cations (Na⁺, NH₄ ⁺, Li⁺, Ba²⁺ and Fe³⁺) was performed in binderless 13X zeolite pellets. Original and cation-exchanged samples were characterized by thermogravimetric analysis coupled with mass spectrometry (inert atmosphere), X-ray powder diffraction and N₂ adsorption/desorption isotherms at 77 K. Despite the presence of other cations than Na (as revealed in TG-MS), crystalline structure and textural properties were not significantly altered upon ion-exchange. Single component equilibrium adsorption isotherms of carbon dioxide (CO₂) and methane (CH₄) were measured for all samples up to 10 bar at 298 and 348 K using a magnetic suspension balance. All of these isotherms are type Ia and maximum adsorption capacities decrease in the order Li > Na > NH₄–Ba > Fe for CO₂ and NH₄–Na > Li > Ba for CH₄. In addition to that, equilibrium adsorption data were measured for CO₂/CH₄ mixtures for representative compositions of biogas (50 % each gas, in vol.) and natural gas (30 %/70 %, in vol.) in order to assess CO₂ selectivity in such scenarios. The application of the Extended Sips Model for samples BaX and NaX led to an overall better agreement with experimental data of binary gas adsorption as compared to the Extended Langmuir Model. Fresh sample LiX show promise to be a better adsorption than NaX for pressure swing separation (CO₂/CH₄), due to its higher working capacity, selectivity and lower adsorption enthalpy. Nevertheless, cation stability for both this samples and NH₄X should be further investigated.     

Searching blue-shifted O–H···Y hydrogen bond in CH<Subscript>3</Subscript>OH complexes with CF<Subscript>4</Subscript>, C<Subscript>2</Subscript>F<Subscript>2</Subscript>, OC,Ne, and He: a theoretical study

The hydrogen-bonded structures of the CH₃OH complexes with CF₄, C₂F₂, OC, Ne, and He are designated as the starting points for geometry optimizations without and with counterpoise (CP) correction at MP2 level of theory with the basis sets 6-31+G*, 6-31++G**, and 6-311++G**, respectively. Tight convergence criteria are applied throughout all geometry optimizations in order to reduce the computational errors. According to the optimizations without CP correction, a blue-shifted O–H···Y (where Y = F, O, Ne, or He) hydrogen bond exists in all these five complexes. The magnitudes of blue shifts of ν(O–H) of the former four complexes with respect to that of CH₃OH are reduced greatly when the polarization and diffuse functions of the hydrogen atoms are added (results from 6-31+G* versus those from 6-31++G**). However, for the complexes CH₃OH–CF₄ and CH₃OH–C₂F₂, our optimizations using the CP corrections did not find the hydrogen-bonded structure to be a stationary point. The energy minimum of both the complexes corresponds to a non-hydrogen-bonded structure.     

The Reactions of Two New Alkoxy-silyl Functionalized Alkynes with M<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> {M = Fe,Ru} and Co<Subscript>2</Subscript>(CO)<Subscript>8</Subscript>. Spectroscopic Identification of the Products

The new alkoxysilyl-functionalized alkynes [HC≡CCH₂N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] and [HC≡C(C₆H₄)–N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] have been synthesized using literature methods. These have been reacted with Fe₃(CO)₁₂, Ru₃(CO)₁₂ and Co₂(CO)₈. With the iron carbonyl only decomposition was observed: with Ru₃(CO)₁₂ splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃], (μ-H)Ru₃(CO)₉[C–C(C₆H₄)NH₂] and (μ-H)₂Ru₃(CO)₉[HC–CCH₃] occurred. Finally, with Co₂(CO)₈ formation of complexes Co₂(CO)₆(HC₂R) R=(C₆H₄)NH₂, CH₂NH(CO)NH(CH₂)₃Si(OEt)₃, (C₆H₄)NH(CO)NH(CH₂)₃Si(OEt)₃ containing the intact alkynes could be obtained.     

Effect of sodium cation on the electrochemical reduction of CO<Subscript>2</Subscript> at a copper electrode in methanol

The electrochemical reduction of CO₂ with a Cu electrode in methanol was investigated with sodium hydroxide supporting salt. A divided H-type cell was employed; the supporting electrolytes were 80 mmol dm⁻³ sodium hydroxide in methanol (catholyte) and 300 mmol dm⁻³ potassium hydroxide in methanol (anolyte). The main products from CO₂ were methane, ethylene, carbon monoxide, and formic acid. The maximum current efficiency for hydrocarbons (methane and ethylene) was 80.6%, at −4.0 V vs Ag/AgCl, saturated KCl. The ratio of current efficiency for methane/ethylene, r _f(CH₄)/r _f(C₂H₄), was similar to those obtained in LiOH/methanol-based electrolyte and larger relative to those in methanol using KOH, RbOH, and CsOH supporting salts. In NaOH/methanol-based electrolyte, the efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was suppressed to below 4%. The electrochemical CO₂ reduction to methane may be able to proceed efficiently in a hydrophilic environment near the electrode surface provided by sodium cation.     

Direct Mass Spectrometric Study of the Ionic Species Content of a C<Subscript>2</Subscript>HCl<Subscript>3</Subscript>/He/O<Subscript>2</Subscript> Microwave Discharge Plasma

Direct on-line studies of a C₂HCl₃/He/O₂ microwave discharge plasma made possible the evolution and detection of many unfamiliar ionic species. Numerous ionic chlorocarbons, chlorohydrocarbons, oxygenated chlorohydrocarbons, oxygenated hydrocarbon radicals, and simple hydrocarbon species were identified mass spectrometrically as by-products: C _m Cl _n (m = 1–4, 6, 8; n = 1–8), C _m H _n Cl _x (m = 1–4, 6, 7, 10; n, x = 1–6), C _m H _n Cl _x O _y (m = 1–5, 12; n = 1–7; x = 1, 2, 4, 6; y = 1–3), C _n H_2n−1O (n = 2, 3), C _m H _n (m = 2, 4, 6, 8; n = 2, 4), and so on. The studies clearly showed the presence of various unfamiliar positive ionic O-containing species such as C₂ClO₂, CCl₃CO, C₂H₂Cl₄O₂, and C₄H₂Cl₆O₃. It is apparent that positive-ion reactions play a significant role in producing many ionic species in the chemistry of C₂HCl₃ plasmas.     

Photochemical arene exchange in the naphthalene complex [CpRu(η<Superscript>6</Superscript>-C <Subscript>10</Subscript>H<Subscript>8</Subscript>)]<Superscript>+</Superscript>

The cation [CpRu(η⁶-C₁₀H₈)]⁺ was shown to exchange naphthalene for other arenes under visible-light irradiation to form the complexes [CpRu (η⁶-arene)]⁺ (arene = C₆H₆, 1,4-C₆H₄Me₂, 1,3,5-C₆H₃Me₃, or 1,2,4,5-C ₆H₂Me₄) in 70–95% yields. The reaction rate of exchange decreases in the series arene = 1,4-C₆H₄Me₂ > C₆H₆ > 1,3,5-C₆H₃Me₃ > 1,2,4,5-C ₆H₂Me₄ >> C₆Me₆ and increases with the coordinating ability of the solvent in the order CH₂Cl₂ < THF—CH₂Cl₂ mixture (1: 1) < acetone.     

Common Intersection Points of Bulk Modulus for Liquefied Natural Gas (LNG) Mixtures

During recent developments on the theories and experimental techniques of compressed liquids and liquid mixtures, it has been revealed that there exist some regularities. Among these, the regularity found by Huang and O'Connell is that the isotherms of reduced bulk modulus of compressed liquids as a function of molar volume intersect at a common point. This intersection is a useful tool for evaluating the reliability of an equation of state (EOS) for producing equilibrium properties of matter. This paper also deals with an extension of the above regularity to some liquefied natural gas (LNG) mixtures including: N₂+CH₄, N₂+C₂H₆, CH₄+C₂H₆, CH₄+C₃H₈, and CH₄+C₄H₁₀ at different temperatures. The present work gives a theoretical analysis for the common bulk modulus point in terms of a statistical‐mechanical equation of state for mixtures. In addition, we have calculated excess molar volume of N₂+CH₄ mixture in terms of temperature and compared it with experimental values.     

Oxygen- versus carbon-coordination of the alpha-stabilized phosphorus ylide Ph<Subscript>3</Subscript>P=C(H)R in palladacycles bearing secondary amines

The ortho-metalated complex [Pd(x){κ ² (C,N)-[C₆H₄CH₂NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)₂ and secondary benzylamine [a, EtNHCH₂Ph; b, t-BuNHCH₂Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ ² (C,N)-[C₆H₄CH₂NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph₃P=C(H)COC₆H₄-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C₆H₄C=CHPPh₃){κ ² (C,N)-[C₆H₄CH₂NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques.     

Synthesis and properties of pentamethylmetallocene derivatives Cp*MCp (M = Ru, Fe). Crystal structure of the salt [CpRuC5Me4CH2+OC6H2(NO2)3-]

Photolysis of a solution of Cp*RuCp (1) in CF₃CO₂H generates salt [CpRu(C₅Me₄CH₂)]-(O₂CCF₃)(2 • O₂CCF₃). The reaction of compound 1 with oleum at 20 °C through the intermediate dication [η⁵-(CH₂C₅Me₄)Ru(μ:η⁵,ν⁵-C₅H₄C₅H₅)Ru(C₅Me₄CH₂)-η⁶]²⁺ leads to the triply charged cation η⁷CH₂)₂C₅Me₃Ru(μη⁵,η⁵-C₅H₄C₅H₄)Ru(C₅Me₄CH₂)-η⁶]³⁺. Synthesis of pentamethylmetallocene derivatives CpMC₅Me₄X (M = Ru, Fe; X = CHO, CH₂OH, CH₂An) has been accomplished. The reactions of 1-hydroxymethyl-2,3,4,5-tetramethylruthenocene with acids CF₃CO₂H, HBF₄, CF₃CO₂H/NaB[C₆H₃(CF₃)₂]₄, and picric acid C₆H₂(NO₂)₃OH afforded salts 2•X (X = CF₃CO₂, BF₄, B[C₆H₃(CF₃)₂]₄), and (2,3,4,5-tetram ethylruthenocenyl)methyl picrate [CpRu(C₅Me₄CH₂)-η⁶][(C₆H₂(NO₂)₃O] (2•C₆H₂(NO₂)₃O). Structure of the latter was characterized by single crystal X-ray diffraction.     

On the state of CH<Subscript>4</Subscript> molecule in the octahedral void of C<Subscript>60</Subscript> fullerite

Methane-intercalated fullerite (CH₄)_0.56C₆₀ was obtained by low-temperature precipitation from solution. Methane transition from the gas phase to the octahedral void of fullerite is accompanied by a bathochromic shift of normal vibrational frequencies (by 19 and 8 cm⁻¹ for ν₃ and ν₄, respectively). The methane ¹³C signal in the proton decoupling ¹³C NMR spectrum is observed as a singlet at δ−0.42. According to quantum chemical calculations using density functional theory, location of methane in the octahedral void of fullerite (C₆₀)₆ leads to a decrease in the total energy of fullerite by 4 kcal mol⁻¹.     

Reactions of [Cp*Ru(H<Subscript>2</Subscript>O)(NBD)]<Superscript>+</Superscript> with diynes

Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)][BF₄] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] is suggested. Graphical Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)]BF₄ (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] was suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.