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1.
UV, IR, and NMR spectra of photolysis products obtained by irradiation of MoH4(Ph2PCH2CH2PPh2)2 (1) in an atmosphere of CO2,13CO2, or C18O2 were studied. In the coordination sphere of1, photochemical reduction of carbon dioxide occurs, yielding products of formate type. Treatment of photoproducts with acids affords formaldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2043–2045, October, 1995.The author is grateful to A. P. Borisov and V. D. Makhaev for providing a sample of MoH4(Ph2PCH2CH2PPh2)2.  相似文献   

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The frustrated Lewis pair Mes(2)PCH(2)CH(2)B(C(6)F(5))(2) reacts readily with 6-dimethylamino-6-methylfulvene at room temperature to yield the trans-1-[B(C(6)F(5))(2)]-2-[CH(2)CH(2)PMes(2)] disubstituted fulvene derivative 9 that features an internal N-B contact. Thermolysis (80 °C in toluene) results in a complete isomerization to the respective 1-[B(C(6)F(5))(2)]-3-[CH(2)CH(2)PMes(2)] isomer 10. Both compounds were characterized by using X-ray diffraction. A reaction scheme is formulated to rationalize the specific formation of these compounds, involving a retro-hydroboration/hydroboration sequence. The reaction of the 6-dimethylaminofulvene with HB(C(6)F(5))(2) yielded the corresponding parent compound 13 that was also characterized by X-ray diffraction.  相似文献   

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Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

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The reactions of methylenecyclopropanes (MCPs) and epoxides with alcohols and aromatic amines can be carried out in supercritical carbon dioxide (scCO2) or modified scCO2 with perfluorocarbon which offer a way to synthesize various alcohols, amino-alcohols, homoallylic ethers, and amines under an environmentally benign condition.  相似文献   

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In this paper the equilibrium solubility of carbon dioxide in 1.0 M, 2.0 M and 4.0 M 2(methylamino)ethanol (MAE) is measured at 303, 313 and 333 K, and at CO2 partial pressures ranging from 1 to 100 kPa using stirred cell reactor. The Kent-Eisenberg model was used to predict the solubility of carbon dioxide in MAE solutions. The equilibrium constant representing hydrolysis of carbamate ion is correlated with temperature, CO2 partial pressure and amine concentration by non-linear regression, using experimental results of carbamate ion concentrations. The model predicted results showed good agreement with the experimental solubility results. The solubility profile of CO2 in MAE showed better performance when compared with other commercial amines.  相似文献   

6.
Using a frustrated Lewis pair approach, the 1,1-bis-(C(6)F(5))(2)BOB(C(6)F(5))(2) is shown to bind CO(2) in a monodentate fashion, while the bis-boranes (X(2)B)(2)C=CMe(2) (X = Cl, C(6)F(5)) give bidentate chelation of CO(2) affording unique heterocycles.  相似文献   

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In spite of wide interest in CO(2) clusters, only dimers and trimers have previously been assigned to specific infrared bands. Here, transitions for clusters with 6-13 molecules are identified in the ν(3) region (~2350 cm(-1)). Spectra are observed in a supersonic jet (T ~ 2.5 K) using a tunable laser probe, and analyzed with the aid of cluster calculations based on a widely-used model potential. Vibrational origins show blue-shifts significantly larger than predicted by resonant dipole interactions.  相似文献   

15.
The extremely sterically hindered borane tris(2,2',2'-perfluorobiphenyl)borane (PBB) has been structurally characterised. In combination with bulky nitrogen bases, it forms the 'frustrated Lewis pairs' (FLPs) PBB/2,2,6,6-tetramethylpiperidine (TMP) (1), PBB/1,4-diazobicyclo[2.2.2]-octane (DABCO) (2) and PBB/2,6-lutidine (lut) (3). These novel, unquenched acid-base pairs have been shown to effect facile room temperature heterolytic cleavage of dihydrogen to form the ammonium borate salts [2,2,6,6-Me(4)C(5)H(6)NH(2)][HB(C(12)F(9))(3)] (4) and [N(C(2)H(4))(3)NH][HB(C(12)F(9))(3)] (5), and lutidinium borate [2,6-Me(2)C(5)H(3)NH][HB(C(12)F(9))(3)] (6). Although these reactions are equilibria, the reverse reaction and release of hydrogen gas was not apparent at temperatures up to 120 °C. The relative Lewis acidity of PBB has been determined using the Gutmann-Beckett method.  相似文献   

16.
Allylation reagents, which possess geminal bis-trimethylsilyl substitution, are readily prepared from E- or Z-alkenyl bromides. The reactivity of 3,3-bis(trimethylsilyl)-2-methyl-1-propene (1) is described and predominantly provides ene reactions with aldehydes to give alcohol 2 in the presence of BF3.OEt2. Alternatively, Sakurai allylation reactions of 1 are observed by using stronger Lewis acids in methylene chloride to exclusively yield E-trisubstituted alkenylsilanes 3.  相似文献   

17.
Binary vapor–liquid equilibrium data were measured for the carbon dioxide (CO2) + 2,2-dichloro-1,1,1-trifluoroethane (R123) system and the carbon dioxide (CO2) + 1-chloro-1,2,2,2-tetrafluoroethane (R124) system at temperature from 313.15 to 333.15 K. These experiments were carried out with a circulating-type apparatus with on-line gas chromatography. The experimental data were correlated well by Peng–Robinson equation of state using the Wong–Sandler mixing rules.  相似文献   

18.
A polystyrene-supported Lewis acidic iron-containing ionic liquid was proved to be recyclable and efficient heterogeneous catalyst for converting CO2 into cyclic carbonate without utilization of any organic solvent or additive. Excellent yields and selectivity were obtained under mild reaction conditions. Notably, the catalyst could be readily recovered and reused over five times without appreciable loss of catalytic activity. A possible catalytic cycle was proposed. The present protocol has successfully been applied to reactions of aziridines/propargyl amines with CO2. This kind of the catalyst presented herein would have great potential in industrial application thanks to its featured advantages.  相似文献   

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