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1.
B. A. Arbuzov N. A. Polezhaeva A. M. Polozov A. A. Mustafin E. I. Goldfarb A. A. Levin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The photochemical, thermo-catalytical and thermal reactions of diazoalkanes with dialkyl (thio)phosphites were studied. Thus, the photolysis of dimethyldiazomalonate and methyl-diazoacetate with dialkyl(thio)phosphites gives P-H insertion products only upon triplet-sensitized conditions (i), whereas diphenyldiazomethane gives P-H insertion products upon direct photolysis as well (ii). The investigation of 31 the reaction mechanism is based on CIDNP 31P method. The catalytical reactions (iii) are a convenient method of preparing (thio)phosphonates. 相似文献
2.
Camacho-Camacho C Biesemans M Van Poeck M Mercier FA Willem R Darriet-Jambert K Jousseaume B Toupance T Schneider U Gerigk U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2455-2461
Insoluble polystyrene grafted compounds of the type (P-H)(1-t){P-(CH2)n SnBu(p)Cl(3-p)}(t), (P-H)(1-t){P-(CH2)n SnBuO}(t) and (P-H)(1-t)[{P-(CH2)n SnBuCl}2O](t/2), in which (P-H) is a cross-linked polystyrene; n=4, 6, and 11; p=0 and 1; and t the degree of functionalisation, were synthesised from Amberlite XE-305, a polystyrene cross-linked with divinylbenzene. The compounds were characterised by using elemental analysis, and IR, Raman, solid-state 117Sn NMR, and 1H and 119Sn high-resolution MAS NMR spectroscopy. The influence of the spacer length and the tin functionality on the catalytic activity of these compounds, as well as their recycling ability, was assessed in the transesterification reaction of ethyl acetate with various alcohols. These studies showed significant differences in the activity of the catalysts interpreted in terms of changes in the mobility of the catalytic centres. Some of the supported catalysts could be recycled at least seven times without noticeable loss of activity. The residual tin content in the reaction products was found to be as low as 3 ppm. 相似文献
3.
Del Bene JE 《The journal of physical chemistry. A》2007,111(25):5509-5514
Ab-initio MP2/aug'-cc-pVTZ calculations have been performed to determine the structures and binding energies of proton-bound complexes stabilized by N-H+-P hydrogen bonds and to investigate the nature of the proton-transfer coordinate in these systems. Double minima are found only when the difference between the protonation energies of the N and P bases is less than about 4 kcal/mol. The isomer in which the protonated nitrogen base is the donor lies lower on the potential surface and also has a greater binding energy relative to the corresponding isolated monomers. Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculations have been employed to obtain one- and two-bond spin-spin coupling constants across these hydrogen bonds. Two-bond coupling constants (2h)J(N-P) correlate with N-P distances, irrespective of whether the donor ion is N-H+ or P-H+. One-bond coupling constants (1)J(N-H) and (1h)J(H-P) for complexes stabilized by N-H+...P hydrogen bonds correlate with corresponding distances, but similar correlations are not found for (1)J(P-H) and (1h)J(H-N) for complexes with P-H+...N hydrogen bonds. Negative values of (1h)K(H-N) and (1h)K(H-P) indicate that the hydrogen bonds in these complexes are traditional. Comparisons are made with complexes stabilized by N-H+-N and P-H+-P hydrogen bonds. 相似文献
4.
B. A. Arbuzov N. A. Polezhaeva A. M. Polozov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract Unlike of the Cu(II) catalysed thermal decomposition of 2-diazo-I,3-dicarbonyl compounds(I) in dialkyl phosphites that results in the formation of 2-phosphono-I,3-dicarbonyl compounds (II,X_C)I, the photosensitized process affords also thiophosphono analogs of the latter (II,X_S) while carried out in dialkyl thio-phosphites. Since there are no P-H insertion products(II) formed on the direct photolysis of I it seems reasonable to suggest that it is the triplet carbene as intermediate that is needed for their formation. Yields of II, which proved to be rather photosensitive, are found to depend substantially on the reaction time. The tendency of II to enolization deecreases with replacement of P-O for P-S group. 相似文献
5.
Ab initio MP2/aug'-cc-pVTZ calculations have been performed to determine the structures and binding energies of 22 open and 3 cyclic complexes formed from the sp2 [H(2)C=PH and HP=PH (cis and trans)] and sp3 [PH2(CH3) and PH3] hybridized phosphorus bases and their corresponding protonated ions. EOM-CCSD calculations have been carried out to obtain (31)P-(31)P and (31)P-(1)H coupling constants across P-H+-P hydrogen bonds. Two equilibrium structures with essentially linear hydrogen bonds have been found along the proton-transfer coordinate, except for complexes with P(CH3)H3+ as the proton donor to the sp2 bases. Although the isomer having the conjugate acid of the stronger base as the proton donor lies lower on the potential energy surface, it has a smaller binding energy relative to the corresponding isolated monomers than the isomer with the conjugate acid of the weaker base as the donor. The hydrogen bond of the latter has increased proton-shared character. All of the complexes are stabilized by traditional hydrogen bonds, as indicated by positive values of the reduced coupling constants (2h)K(P-P) and (1)K(P-H), and negative values of (1h)K(H-P). (2h)J(P-P) correlates with the P-P distance, a correlation determined primarily by the nature of the proton donor. For open complexes, (1)J(P-H) always increases relative to the isolated monomer, while (1h)J(H-P) is relatively small and negative. (2h)J(P-P) values are quite large in open complexes, but are much smaller in cyclic complexes in which the P-H+-P hydrogen bonds are nonlinear. Thus, experimental measurements of (2h)J(P-P) should be able to differentiate between open and cyclic complexes. 相似文献
6.
R. R. Shagidullin L. Kh. Ashrafullina N. I. Monakhova S. A. Terent'eva 《Russian Chemical Bulletin》1990,39(3):489-491
Data on the integral intensities of the v(P-H) bands of di-n-propyl phosphite and diisopropyl phosphite in different media have shown that in strong protonacceptor solvents the P-H group of the dialkyl phosphites examined is able to form weak hydrogen bonds. Beside this, association of liquid di-n-propyl and diisopropyl phosphites takes place by a dipole-dipole mechanism. Variations in the spectra as the medium, the temperature, and the phase are varied point to conformational nonuniformity in the di-n-propyl and diisopropyl phosphite molecules. The (P-H) band is conformationally sensitive. In the crystal, a less polar, gauche, gauche form is achieved.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 564–567, March, 1990. 相似文献
7.
A variational method has been used with Gaussian orbitals to calculate the susceptibilities of localized P-H and P-C bonds in PH3 and P(CH3)3. An additive scheme has been used with localized molecular fragments to determine the susceptibility and proton screening, where the values agree well with experiment. Diagrams for nuclear magnetic isoscreening lines for the P-H and P-C bonds have been calculated.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 4, pp. 487–491, July–August, 1986. 相似文献
8.
The reactions of Group 8, 9 and 10 monocations with phosphane were studied under single-collision conditions in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Fe(+) is completely unreactive, Co(+) reacts slowly and shows both adduct formation and P-H bond activation, and Ni(+) reacts slowly as well but shows adduct formation only. In contrast to their first-row congeners, the investigated second- and third-row transition metal monocations show facile P-H bond activations. Remarkably, extensive dehydrogenations of the collision complexes yield cations MPH(+), MP(2) (+), MP(3)H(+), MP(4) (+) and so on. Exceptional behaviour is shown by the two d(9) cations palladium (whose "dehydrogenation power" is rather limited) and platinum (which gives rise to a great manifold of only partially dehydrogenated species as well). Collision-induced dissociation experiments suggest that P(2) and PH units are formed as ligands. 相似文献
9.
Guo Yi Bai Yong Hui Yang Zheng Ma Jian Zhong Xu Man De Qiu Fei He Xi Long Yan Hai Yang Dou 《Research on Chemical Intermediates》2012,38(3-5):795-806
Friedel?CCrafts acylation of pyrrole with acetic anhydride was studied over different zeolites and an ultrasonic-assisted phosphoric acid-modified H?? (P-H??-US) zeolite was found to have the best catalytic performance among all the zeolites examined. The conversion of acetic anhydride reached 98.8% and the selectivity to acetylpyrroles was 97.0% under the optimized conditions. The high activity of the P-H??-US zeolite is attributed to the increase of weak acid sites, caused by the synergistic effect between the phosphoric acid modification and ultrasound. Moreover, the carbonaceous deposits, mainly due to the adsorption of reactants and products, on the surface acid sites and the blockage of the pores is believed to be the reason for the deactivation of the reused P-H??-US zeolite, confirmed from the Brunauer?CEmmett?CTeller (BET) method, scanning electron microscopy, and X-ray photoelectron spectroscopy. Furthermore, the catalyst activity can be recovered effectively by a subsequent calcination. 相似文献
10.
Ananikov VP Makarov AV Beletskaya IP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12623-12630
The puzzling question of alkyne insertion into Pd-P and Pd-H bonds leading to the formation of new Pd-C, C-P, and C-H bonds was explored by theoretical calculations at the CCSD(T) and B3LYP levels of theory. The key factors responsible for selectivity of catalytic hydrofunctionalization of alkynes were resolved and studied in details for the models of hydrophosphorylation, hydrophosphinylation, and hydrophospination reactions. In contrast with the generally accepted mechanistic picture, the calculations have shown that several pathways are possible depending on the nature and geometrical arrangement of the phosphorus group. It was found that the product of alkyne insertion into the metal-hydrogen bond should be easily formed under kinetic-control conditions, while the product of alkyne insertion into the metal-phosphorus bond may be formed in certain cases under thermodynamic control. For the first time, the calculations have revealed the role of the oxygen atom in the reactivity of P=P(O)R(2) groups and the role of the interactions involving the lone pair of the P=PR(2) group in the reagent. The fundamental properties of the Pd-P, C-P, and P-H bonds were reported, and the larger bond strength upon increasing the number of oxygen atoms bound to phosphorus (P=PR(2), P(O)R(2), and P(O)(OR)(2)) have been shown. The relationship between bond energy, acidity, and reactivity of the studied phosphorus compounds has been determined. 相似文献
11.
Ab initio calculations at the MP2/aug'-cc-pVTZ level have been carried out to investigate the structures and binding energies of cationic complexes involving protonated sp, sp2, and sp3 phosphorus bases as proton donor ions and the sp-hybridized phosphorus bases H-C[triple bond]P and H3C-C[triple bond]P as proton acceptors. These proton-bound complexes exhibit a variety of structural motifs, but all are stabilized by interactions that occur through the pi cloud of the acceptor base. The binding energies of these complexes range from 6 to 15 kcal/mol. Corresponding complexes with H3C-C[triple bond]P as the proton acceptor are more stable than those with H-C[triple bond]P as the acceptor, a reflection of the greater basicity of H3C-C[triple bond]P. In most complexes with sp2- or sp3-hybridized P-H donor ions, the P-H bond lengthens and the P-H stretching frequency is red-shifted relative to the corresponding monomers. Complex formation also leads to a lengthening of the C[triple bond]P bond and a red shift of the C[triple bond]P stretching vibration. The two-bond coupling constants 2pihJ(P-P) and 2pihJ(P-C) are significantly smaller than 2hJ(P-P) and 2hJ(P-C) for complexes in which hydrogen bonding occurs through lone pairs of electrons on P or C. This reflects the absence of significant s electron density in the hydrogen-bonding regions of these pi complexes. 相似文献
12.
Conclusion The addition of carbonyl compounds to trimethylsilylphenylphosphine gives adducts with a P-H bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1417–1419, June, 1982. 相似文献
13.
A Parabola-Hyperbola (P-H) kinetic model for NR sulphur vulcanization is presented. The idea originates from the fitting composite Parabola-Parabola-Hyperbola (P-P-H) function used by the authors in [1,2] to approximate experimental rheometer curves with the knowledge of a few key parameters of vulcanization, such as the scorch point, initial vulcanization rate, 90% of vulcanization, maximum point and reversion percentage. After proper normalization of experimental data (i.e. excluding induction and normalizing against maximum torque), the P-P-H model reduces to the discussed P-H composite function, which is linked to the kinetic scheme originally proposed by Han and co-workers [3]. Typically, it is characterized by three kinetic constants, where classically the first two describe incipient curing and stable/instable crosslinks and the last reproduces reversion.The powerfulness of the proposed approach stands into the very reduced number of input parameters required to accurately fit normalized experimental data (i.e. rate of vulcanization at scorch, vulcanization at 90%, maximum point and reversion percentage), and the translation of a mere geometric data-fitting into a kinetic model. Kinetic constants knowledge from simple geometric fitting allows characterizing rubber curing also at temperature different from those experimentally tested.The P-H model can be applied also in the so-called backward direction, i.e. assuming Han's kinetic constants known from other models and deriving the geometric fitting parameters as result.Some existing experimental data available, relying into rheometer curves conducted at 5 different temperatures on the same rubber blend are used to benchmark the P-H kinetic approach proposed, in both backward and forward direction. Very good agreement with previously presented kinetic approaches and experimental data is observed. 相似文献
14.
We report the first rotationally resolved spectroscopic studies on PH3+(X2A2") using zero kinetic energy photoelectron spectroscopy and coherent VUV radiation. The spectra about 8000 cm(-1) above the ground vibrational state of PH3+(X2A2") have been recorded. We observed the vibrational energy level splittings of PH3+(X2A2") due to the tunneling effect in the inversion (symmetric bending) vibration (nu2+). The energy splitting for the first inversion vibrational state (0+/0-) is 5.8 cm(-1). The inversion vibrational energy levels, rotational constants, and adiabatic ionization energies (IEs) for nu2+ = 0-16 have been determined. The bond angles between the neighboring P-H bonds and the P-H bond lengths are also obtained using the experimentally determined rotational constants. With the increasing of the inversion vibrational excitations (nu2+), the bond lengths (P-H) increase a little and the bond angles (H-P-H) decrease a lot. The inversion vibrational energy levels have also been calculated by using one dimensional potential model and the results are in good agreement with the experimental data for the first several vibrational levels. In addition to inversion vibration, we also observed firstly the other two vibrational modes: the symmetric P-H stretching vibration (nu1+) and the degenerate bending vibration (nu4+). The fundamental frequencies for nu1+ and nu4+ are 2461.6 (+/-2) and 1043.9 (+/-2) cm(-1), respectively. The first IE for PH3 was determined as 79670.9 (+/-1) cm(-1). 相似文献
15.
The abilities of transition metal species to activate P-H and P-P bonds are emerging. Such investigations provide novel M-P species, as well as stoichiometric and catalytic routes to P(III) compounds. The application of organometallic approaches and methodologies to phosphorus chemistry is providing emerging, stoichiometric and catalytic routes to phosphorus compounds and materials. This tutorial review surveys recent advances, with a focus on the activation of P-H and P-P bonds. The isolation of novel M-P species provides insight, while stoichiometric and catalytic reactivity expands the arsenal of synthetic strategies leading to P(III) compounds. 相似文献
16.
By quantumchemical calculations of 1,2-dihydro-1,2-azaphosphorin by semiempirical and abinitio calculations we discovered that in gas phase it has twist form with planar nitrogen and pyramidal phosphorus atoms, the latter with a pseudoaxial substituent. The N-H and P-H bonds occupy anticlinal positions. 相似文献
17.
Biphenyl-2,2'-bisfenchol (BIFOL) based chlorophosphite, BIFOP-Cl, exhibits surprisingly high stabilities against hydrolysis as well as hydridic and organometallic nucleophiles. Chloride substitution in BIFOP-Cl proceeds only under drastic conditions. New enantiopure, sterically demanding phosphorus ligands such as a phosphoramidite, a phosphite and a P-H phosphonite (BIFOP-H) are hereby accessible. In enantioselective Cu-catalyzed 1,4-additions of ZnEt2 to 2-cyclohexen-1-one, this P-H phosphonite (yielding 65% ee) exceeds even the corresponding phosphite and phosphoramidite. 相似文献
18.
Ito S Miyake H Yoshifuji M Höltzl T Veszprémi T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5960-5965
In mixing 2,4,6-tris(2,4,6-tri-tert-butylphenyl)-1,3,6-triphosphafulvene with alkyllithium compounds and acetic acid, both of nucleophilic alkylation and electrophilic protonation occurred at the exo sp2-phosphorus atoms to afford [2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclopentadienylidene](alkyl)(2,4,6-tri-tert-butylphenyl)phosphoranes which are phosphorus ylides that bear a P-H bond. A phosphorus ylide bearing both P-H and P-F bonds was obtained by reaction of 2,4,6-tris(2,4,6-tri-tert-butylphenyl)-1,3,6-triphosphafulvene with hydrogen tetrafluoroborate, and the structure was determined by X-ray crystallography. Both P=C double bond and P(+)-C(-) zwitterionic character was indicated by the metric parameters. The isolated phosphorus ylide bearing a P-H bond, [2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclopentadienylidene](2,4,6-tri-tert-butylphenyl)phosphorane, showed no isomerization by H-migration to the corresponding phosphinodiphospholes, probably due to the pi-accepting ability of the unsaturated PC bonds and aromaticity of the C3P2 ring. The ylide structure and aromaticity of 2,4-diphosphacyclopenta-2,4-dienylidenephosphorane was characterized by theoretical calculations. In addition, the regioselective protonation of the lithiated phosphinodiphospholes generated from the 1,3,6-triphosphafulvene is discussed. 相似文献
19.
Influence of the Inductive Effect of Substituents on the NMR Parameters of Phosphorylated Alkenes 总被引:1,自引:0,他引:1
Cherkasov A. R. Galkin V. I. Sibgatullin I. M. Khusainova N. G. Zyablikova T. A. Buzykin B. I. Cherkasov R. A. 《Russian Journal of General Chemistry》2001,71(3):343-347
The inductive effect model was used to adequately describe and predict the P-H coupling constants in the 1H NMR spectra of phosphorylated alkenes. A procedure was developed for determination of the steric structure of phosphorylated alkenes from the 1H NMR spectra of one of the isomers. 相似文献
20.
Manbeck GF Kohler MC Porter MR Stockland RA 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12595-12606
The susceptibility of a prototypical hydrogen phosphonate to undergo P-H activation upon treatment with alkynylgold complexes has been studied. Dynamic solution behavior was observed during reactions involving triphenylphosphine ligated substrates and was attributed to rapid phosphine exchange between the alkynylgold starting material and the gold phosphonate product. The use of bulky biaryldialkylphosphine ligands eliminated the fluxional behavior, but did not significantly slow the rate of P-H activation. Similarly, changing the supporting ligand to an N-heterocyclic carbene did not significantly slow the rate of the reaction. Despite a number of reports outlining the functionalization of propargyl alcohols using gold catalysts, incorporating these groups into the architecture of the alkynylgold substrates did not alter the product distributions. Although the chemistry tolerated a range of supporting ligands, incorporating electron donating groups into the alkyne increased the rate of the reaction while electron-withdrawing groups slowed the reaction. A possible mechanism for the process includes a transition state containing significant pi-contribution from the alkyne. Due to the high yields of gold phosphonates obtained in this chemistry as well as the mild conditions of the reactions, the interception of intermediates/catalysts by substrates or ligands containing labile P-H donors is an issue that must be circumvented when designing or developing a gold catalyzed reaction that proceeds through alkynylgold intermediates. 相似文献