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1.
E. Yu. Tyulyaeva N. G. Bichan T. N. Lomova A. S. Semeikin 《Russian Journal of Inorganic Chemistry》2017,62(12):1576-1583
The spectral (UV–Vis, IR, and NMR 1H) properties and the state of oxorhenium(V) complexes with 5,15-bis(4′-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphin H2P (O=Re(X)P) in protic solvents have been studied depending on the axial trans-ligand X– (X = Cl, OPh, or OH). The O=Re(Cl)P, O=Re(OPh)P, and O=Re(OH)P in AcOH and CF3COOH are subjected to reaction of substitution their axial ligands with solvent molecules or anions, while remaining stable to the dissociation of M–N bonds and to oxidation both to the macrocyclic ligand and to the central metal cation. Quantitative parameters of the coordination of molecular oxygen by O=Re(Cl)P in 17.4–18.2 M H2SO4 to form O=Re(O2)P+ · Cl– have been obtained, these parameters being independent of the initial H2SO4 concentration. The character of peripheral functional substituents in H2P has been shown to be responsible for the stability of the studied oxo complexes to chemical oxidation in aerated acids. 相似文献
2.
Kai Li Hongjian Sun Wenjing Yang Yajie Wang Shangqing Xie Xiaoyan Li Olaf Fuhr Dieter Fenske 《应用有机金属化学》2020,34(3):e5337
A series of phosphorus-chalcogen chelated hydrido iron (II) complexes 1–7 , (o-(R'2P)-p-R-C6H4Y)FeH (PMe3)3 ( 1 : R = H, R' = Ph, Y = O; 2 : R = Me, R' = Ph, Y = O; 3 : R = H, R' = iPr, Y = O; 4 : R = Me, R' = iPr, Y = O; 5 : R = H, R' = Ph, Y = S; 6 : R = Me, R' = Ph, Y = S; 7 : R = H, R' = Ph, Y = Se), were synthesized. The catalytic performances of 1–7 for dehydration of amides to nitriles were explored by comparing three factors: (1) different chalcogen coordination atoms Y; (2) R' group of the phosphine moiety; (3) R substituent group at the phenyl ring. It is confirmed that 5 with S as coordination atom has the best catalytic activity and 7 with Se as coordination atom has the poorest catalytic activity among complexes 1 , 5 and 7 . Electron-rich complex 4 is the best catalyst among the seven complexes and the dehydration reaction was completed by using 2 mol% catalyst loading at 60 °C with 24 hr in the presence of (EtO)3SiH in THF. Catalyst 4 has good tolerance to many functional groups. Among the seven iron complexes, new complexes 3 and 4 were obtained via the O-H bond activation of the preligands o-iPr2P(C6H4)OH and o-iPr2P-p-Me-(C6H4)OH by Fe(PMe3)4. Both 3 and 4 were characterized by spectroscopic methods and X-ray diffraction analysis. The catalytic mechanism was experimentally studied and also proposed. 相似文献
3.
Reaction of Diphenoxyphosphorylchloride with N,N-disubstituted Ureas – Formation of Phosphorylated Biuret Compounds N′,N′-disubstituted N-diphenoxyphosphorylureas, (PhO)2P(O)? NH? CO? NR1R2 (R1 = R2 = Et, 1 ; n-Pr, 2 ; n-Bu, 3 ; i-Bu, 4 ; R1 = Me and R2 = Ph, 5 ) as well as phosphorylated biuret compounds, (PhO)2P(O)? NH? CO? NH? CO? NR1R2 are obtained in the reaction of diphenoxyphosphorylchloride with N,N-disubstituted ureas and triethylamine. The biuret derivatives are formed via (PhO)2P(O)NCO. Their yield rises if the reaction is carried out without amine. The X-ray crystal structure analysis of (PhO)2P(O)? NH? CO? NH? CO? NPr2, 8 , shows that dimers exist in the crystal with intermolecular as well as intramolecular hydrogen bonds. The framework formed by atoms P? N1? C1(O4)? N2? C2(O5)? N3(C3)C6 is planar. The existence of a rotation barrier along the bond C2–N3 was detected by NMR spectroscopy. 相似文献
4.
Yo Ueda K
ichi Mori Keiki Kouno Tokihiro Nhya 《Journal of mass spectrometry : JMS》1976,11(10):1027-1036
The mass spectra of 30 sulfinamide derivatives (RSONHR', R' alkyl or p-XC6H4) are reported. Most of the spectra had peaks attributable to thermal decomposition products. For some compounds these were identified by pyrolysis under similar conditions to be: RSO2NHR', RSO2SR, RSSR and NH2R' (in all kinds of sulfinyl amides); RSNHR' (in the case of arylsulfinyl arylamides); RSO2C6H4NH2, RSOC6H4NH2 and RSC6H4NH2 (in the case of arylsulfinyl arylamides of the type of X = H) The mass spectra of the three thermally stable compounds showed that there are several kinds of common fragment ions. The mass spectra of the thermally labile compounds had two groups of ions; (i) characteristic fragment ions of the intact molecules and (ii) the molecular ions of the thermal decomposition products. It was concluded that the sulfinamides give the following ions after electron impact: [M]+, [M ? R]+, [M ? R + H]+, [M ? SO]+, [RS]+, [NHR']+, [NHR' + H]+, [RSO]+, [RSO + H]+, [R]+, [R + H]+, [R']+ and [M ? OH]+, and that the thermal decomposition products give the following ions: [RSO2SR]+, [RSSR]+, [M ? O]+, [M + O]+ and [RSOC6H4NH2]+. 相似文献
5.
John S. Field Raymond J. Haines Elsie Meintjies Beate Sigwarth Petrus H. Van Rooyen 《Journal of organometallic chemistry》1984,268(2):c43-c47
Treatment of [Rh2Cl2(CO)2 {μ-(PhO)2PN(Et)P(OPh)2}2] with various reducing agents gives a number of products, the type depending on the conditions employed. The products isolated include [Rh2(CO)2{μ-(PhO)2PN(Et)P(OPh)2}2], [Rh2(CO)3{μ-(PhO)2PN(Et)P(OPh)2}2],and [Rh2HgCl(μ-H)(CO)2{μ-(PhO)2PN(Et)P(OPh)2}2]; the structure of the last complex was determined by X-ray diffraction. 相似文献
6.
Masami Kamigaito Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):2987-2994
Phosphoric and phosphinic acid derivatives (R1R2PO2H; R1, R2 = OPh, OPh; OnBu, OnBu; Ph, Ph; Ph, H) in conjunction with zinc chloride (ZnCl2) led to living cationic polymerization of isobutyl vinyl ether (IBVE) in toluene below 0°C. The number-average molecular weights (M?n) of the polymers (M?n > 2 × 104) were directly proportional to monomer conversion and in excellent agreement with the calculated values assuming that one polymer chain forms per R1R2PO2H molecule. Throughout the reaction, the molecular weight distributions (MWDs) stayed narrow (M?w/M?n ? 1.1). A dibasic acid, PhOP (O) (OH)2, coupled with ZnCl2, also induced living cationic polymerization of IBVE where one molecule of the acid generated two living polymer chains. The polymerization by (PhO)2PO2H/ZnCl2 and its model reactions were directly analyzed by 31P and 1H-NMR spectroscopy. The analysis showed that the acid initially forms the adduct [CH3CH(OiBu)OP(O)(OPh)2], the phosphate linkage of which is in turn activated by ZnCl2 so as to initiate living propagation. The finding thus indicates that (PhO)2PO2H indeed acts as an initiator in the living polymerization. The NMR analysis also suggested that an exchange reaction occurs between the phosphate group at the polymer terminal and the chlorine in ZnCl2. The occurrence of living IBVE polymerization with these various R1R2PO2H/ZnCl2 systems shows that phosphoric and phosphinic acids are another general class of protonic acids which are effective initiators for the living cationic polymerization assisted by Lewis acids. © 1993 John Wiley & Sons, Inc. 相似文献
7.
Colin Eaborn 《Journal of organometallic chemistry》1981,218(1):C19-C21
X-ray diffraction shows that [Rh2(CO)3{(PhO)2 PN(Et)P(OPh)2}2], synthesised by reduction of [{RhCl(CO)(PhO)2PN(Et)P(OPh)2}2] with amalgamated zinc in the presence of carbon monoxide, has an unusual structure with one rhodium atom square planar and the other trigonal bipyramidal. 相似文献
8.
Replacement and Oxidation Reactions of N-Dichlorophosphanyl Triphenylphosphazene, Ph3P?N? PCl2 The title compound ( 1 ) reacts with MeOH, EtOH, PhOH, EtSH, and water forming N-phosphanyl or N-phosphinoyl phosphazenes, resp., Ph3P?N? PX2 (X ? OPh( 8 ), SEt( 9 )) or Ph3P?N? PH(O)X (X ? Cl( 3 ), OH( 4 ), OMe( 5 ), OEt( 7 )). The reaction of 1 with P(NEt2)3 yields Ph3P?N? P(NEt2)2 ( 10 ). Ph3P?N? PF2( 11 ) and Ph3P?N? PH(O)F ( 12 ) are obtained by chlorine-fluorine exchange. The N-phosphanyl compounds 1 , 8 , 9 and 11 are oxidized by NO2 yielding the corresponding N-phosphoryl derivatives, Ph3P?N? P(O)X2 (X ? Cl( 2 ), OPh( 13 ), SEt ( 14 ), F( 15 )). The thiophosphoryl compounds, (Ph3P?N? P(S)X2 (X ? Cl( 16 ), OPh( 17 ), F( 18 )) are obtained by oxidizing 1 , 8 , and 11 with sulfur. 相似文献
9.
Oksana V. Midyanko Vasilii Yu. Galla Vladimir M. Buzash Vukadin M. Leovac 《Transition Metal Chemistry》1990,15(2):96-98
Summary The reaction of aqueous solutions of 3d metal salts with bis(hydroxylammonium) bicyclo[2.2.1]-hept-5-en-endo-2,3-cis-dicarboxylate in a 12 mole ratio yielded complexes of the general formula [MnL2(NH3OH)2]·nH2O and [FeIIIL2(NH3OH)H2O]·H2O, where MII=Mn, Fe, Co, Ni, Cu and Zn, and L=bicyclo[2.2.1]-hept-5-en-endo-2,3-cis-dicarboxylate dianion.The compounds were characterized by i.r. spectra and thermal analysis. For all complexes, an octahedral structure is proposed which is formed bytrans coordination of two bidentate (OO) ligands (L) and two NH3OH+ cations attrans positions, coordinated also through oxygen atoms; and similarlytrans positions for NH3OH+ and H2O in the case of the FeIII complex. 相似文献
10.
A novel hydrated cobalt tetraborate complex NH4[Co(NH3)5(H2O)][B4O5(OH)4]2·6H2O, was synthesized by the reaction of NH4‐borate aqueous with CoCl2 and its structure was determined by single crystal X‐ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a=1.2901(2) nm, b=1.6817(3) nm, c=1.1368(2) nm, α=β=γ=90°, V=2.4742(8) nm3, and Z=4. This compound contains infinite borate layers constructed from [B4O5(OH)4]2? units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co(NH3)5(H2O)]3+ groups through hydrogen bonds to form 3D framework. The groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra (4000–400 cm?1) of NH4[Co(NH3)5(H2O)][B4O5(OH)4]2·6H2O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The middle band observed at 575 cm?1 in Raman spectrum is the pulse vibration of [B4O5(OH)4]2?. 相似文献
11.
Julia Pretula Krzysztof Kaluzynski Blazej Wisniewski Ryszard Szymanski Ton Loontjens Stanislaw Penczek 《Journal of polymer science. Part A, Polymer chemistry》2008,46(3):830-843
Conditions of synthesis of poly(ethylene phosphates) in reaction of H3PO4 with HOCH2CH2OH (EG), the actual path of polycondensation, and structure of the obtained polymers (mostly oligomers) and kinetics of reaction are described. Preliminary kinetic information, based on the comparison of the MALDI‐TOF‐ms and 31P{1H} NMR spectra as a function of conversion is given as well. Because of the dealkylation process fragments derived from di‐ and triethylene glycols are also present in the repeating units. Structures of the end groups (? CH2CH2OH or ? OP(O)(OH)2) depend on the starting ratio of [EG]0/[H3PO4]0, although even at the excess of EG the acidic end groups prevail because of the dealkylation process. In MALDI‐TOF‐ms products with Pn equal up to 21 have been observed. The average polymerization degrees (Pn) are lower and have been calculated from the proportion of the end groups. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 830–843, 2008 相似文献
12.
Dr. Olivier Berger Prof. Jean‐Luc Montchamp 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12385-12388
The intermolecular radical functionalization of arenes with aryl and alkyl H‐phosphinate esters, as well as diphenylphosphine oxide and H‐phosphonate diesters, is described. The novel catalytic MnII/excess MnIV system is a convenient and inexpensive solution to directly convert Csp2?H into C?P bonds. The reaction can be employed to functionalize P‐stereogenic H‐phosphinates since it is stereospecific. With monosubstituted aromatics, the selectivity for para‐substitution increases in the order (RO)2P(O)H<R1P(O)(OR)H<Ph2P(O)H, a trend that may be explained by steric effects. 相似文献
13.
Summary The carbonyl ligands in the Rh1 complexes Rh(L-L)(CO)2 [L-L=anthranilate (AA) orN-phenylanthranilate(FA) ions] are replaced by P(OPh)3 to form the mono-or disubstituted products, Rh(L-L)(CO)[P(OPh)3] and Rh(L-L)[P(OPh)3]2 respectively depending on the [P(OPh)3]/[Rh] molar ratio, at room temperature and in air. Under argon at [P(OPh)3]/[Rh]4 theortho-metallated Rh1 complex Rh[P(OPh)3]3[P(OC6H4)-OPh)2] is formed. The new route forortho-metallated Rh1 complex synthesis is described.The Rh(AA)(CO)2 complex was used as a catalyst precursor in hydroformylation of olefins. 相似文献
14.
Mahdi A. Mohammed Ahmed Fetoh Tamer Awad Ali Magdy M. Youssef Gaber M. Abu El-Reash 《应用有机金属化学》2023,37(1):e6910
Sodium4-hydroxy-3-([2-picolinoylhydrazineylidene]methyl)benzenesulfonate (NaH2PH) was synthesized as a novel water-soluble ligand, by the condensation of picolinohydrazide with sodium 3-formyl-4-hydroxybenzenesulfonate. The (NaH2PH) ligand and its isolated Co (II), Fe (III), Hg (II), and Pd (II) complexes were analyzed by elemental analysis and characterized by spectroscopic (Fourier transform infrared spectroscopy, UV–visible, powder XRD, 1H NMR,13C NMR, MS) and magnetic measurements. By comparing IR spectra of both ligand and the metal complexes, one can assume that the (NaH2PH) ligand behaves as a bi-negative tetradentate (ONNO) in [Co (NaPH)(H2O)2].3H2O, and a mono-negative tridentate (ONO) in [Fe (NaPH)Cl2(H2O)] complex, whereas in [Hg2(NaPH)Cl2(H2O)] complex, (NaH2PH) coordinates as a bi-negative pentadentate (ONNNO) ligand via deprotonated OH group of phenolic ring (C=N)Py and (C=N*) coordinated to one of Hg (II) ion and the oxygen atom of enolic group and (C=N)az group with the another Hg (II) ion. Moreover, (NaH2PH) acts as bi-negative tridentate (ONO) ligand in [Pd (NaPH)(H2O)].2H2O complex. The geometries of complexes were suggested based on the UV–visible spectra, magnetic measurements and confirmed by applying discrete Fourier transform (DFT) optimization studies. The thermal fragmentation of both [Pd (NaPH)(H2O)].2H2O and [Co (NaPH)(H2O)2].3H2O complexes was performed, and the kinetic and thermodynamic parameters were computed using the Coats–Redfern and Horowitz–Metzger methods. The redox behavior of divalent ions of cobalt and mercury were discussed by the cyclic voltammetry technique in the presence and absence of (NaH2PH) ligand. Biological potencies of the ligand and its metal complexes were evaluated as antioxidants (ABTS and DPPH), anticancer, DNA, and antimicrobial (Staphylococcus aureus and Bacillus subtilis as Gram (+) bacteria, Escherichia coli and Pseudomonas aeruginosa as Gram (−) bacteria, and Candida albicans as fungi). 相似文献
15.
Eight disubstituted benzyltin complexes, i.e., {[R(O)C=N‐N=C (Me)COO]R'2Sn(CH3OH)}n ( 1a and 2b ), {[R(O)C=N‐N=C (Me)COO]R'2Sn(CH3OH)}2 ( 1b and 1d ) and {[R(O)C=N‐N=C (Me)COO]R'2Sn}n ( 1c , 2a , 2c , and 2d ) (R = C4H3O‐, C4H3S‐, p–t‐Bu‐C6H4‐ or p‐MeO‐C6H4‐; R' = o‐Cl‐C6H4CH2‐ or o‐Me‐C6H4CH2‐), were prepared from the reaction of arylformylhydrazine, pyruvic acid and disubstituted benzyltin dichloride with microwave irradiation. All complexes were characterized by FT‐IR spectroscopy, 1H, 13C and 119Sn NMR spectroscopy, HRMS, elemental analysis, X‐ray single‐crystal diffraction and TGA. The in vitro antitumour activities of all complexes were evaluated by an MTT assay against three human cancer cell lines (NCI‐H460, HepG2, and MCF7). 2b exhibited strong antitumour activity on HepG2 cells and was expected to be a suitable platform for further chemical optimization to develop as anticancer therapeutics. The DNA binding of 2b was studied by UV–visible absorption spectrometry, fluorescence competitive assays, viscosity measurements and gel electrophoresis. Molecular docking was used to predict the binding between 2b and DNA, and the results show that 2b can become embedded in the double helix of DNA and cleave DNA. 相似文献
16.
《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1980,36(11):997-1001
IR and Raman spectra of solid H3BO, Na[B(OH)4], Na2[B4O5(OH)4]·8H2O, Na[B5O6(OH)4]·3H2O, K[B5O6(OH)4]·2H2O, (NH4)2[B4O5(OH)4]·2H2O, β-NH4[B5O6(OH)4]· 2H2O, NH4[B5O6(OH)4]·.0,67H2O and NH4[B5O6(OH)4] were recorded between 300 and 1550 cm−1 as well as the spectra of H311BO3, H310BO3, Na[11B(OH)4], Na[10B(OH)4], Na2[11B4O5(OH)4]·8H2O, Na2[10B4O5(OH)4]·8H2O, (NH4)2[11B4O5(OH)4]·2H2O, (NH4)2[10B4O5(OH)4]·2H2O, K[11B5O6(OH)4]·2H2O or K[10B5O6(OH)4]·2H2O.The spectra were interpreted by comparisons with known structures, by comparisons within the series, and by interpretations of isotopic shifts. Thus a large number of lines could be assigned, and it was possible to arrive at general hints for the interpretation of the spectra. Finally, a very important and characteristic line called pulsation vibration could be explained. 相似文献
17.
Studies of the stoichiometry and kinetics of the reaction between hydroxylamine and iodine, previously studied in media below pH 3, have been extended to pH 5.5. The stoichiometry over the pH range 3.4–5.5 is 2NH2OH + 2I2 = N2O + 4I? + H2O + 4H+. Since the reaction is first-order in [I2] + [I3?], the specific rate law, k0, is k0 = (k1 + k2/[H+]) {[NH3OH+]0/(1 + Kp[H+])} {1/(1 + KI[I?])}, where [NH3OH+]0 is total initial hydroxylamine concentration, and k1, k2, Kp, and KI are (6.5 ± 0.6) × 105 M?1 s?1, (5.0 ± 0.5) s?1, 1 × 106 M?1, and 725 M?1, respectively. A mechanism taking into account unprotonated hydroxylamine (NH2OH) and molecular iodine (I2) as reactive species, with intermediates NH2OI2?, HNO, NH2O, and I2?, is proposed. 相似文献
18.
Summary Complexes of chromium(II) with diphenylphosphinate, Cr(O2PPh2)2 · H2O, diphenylphosphate Cr{O2P(OPh)2} · 1/2H2O, phenylphosphinate, Cr(O2PHPh)2 · 2H2O, phenyl-phosphonate, Cr(O3PPh) · H2O, and monofluorophosphate, Cr{O2P(OH)F}2 · H2O, are high-spin. From their reflectance spectra and antiferromagnetic behaviour the last three are believed to be three-dimensional polymers with R2PO
2
–
bridges in which some O atoms bridge two Cr atoms, leading to magnetic interaction. The other complexes show only weak magnetic interaction, and the reflectance spectra of Cr(O2PPh2)2 and its hydrate indicate that both contain planar CrO4 units. It is therefore believed to be a linear polymer with the Cr atoms well separated by double R2PO
2
–
bridges. The reflectance spectrum of Cr{O2P(OPh)2}2 suggests additional weak coordination of O atoms from adjacent polymer chains. 相似文献
19.
Kuan Gao Dr. Chao Huang Yan Qiao Shasha Wang Prof. Jie Wu Prof. Hongwei Hou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9499-9502
We report a porous three-dimensional anionic tetrazolium based CuI−MOF 1 , which is capable of cleaving the N−H bond of ammonia and primary amine, as well as the O−H bond of H2O along with spontaneous H2 evolution. In the gas-solid phase reaction of 1 with ammonia and water vapor, CuI−MOF 1 was gradually oxidized to NH2−CuII−MOF and OH−CuII−MOF, through single-crystal-to-single-crystal (SCSC) structural transformations, which was confirmed by XPS, PXRD and X-ray single-crystal diffraction. Density functional theory (DFT) demonstrated that CuI−MOF could lower N−H bond dissociation free energy of ammonia through coordination-induced bond weakening and promote H2 evolution by the reduction potential of 1 . To our knowledge, this is the first example of MOFs that activate ammonia and amine in gas-solid manner. 相似文献
20.
Vadapalli Chandrasekhar Viswanathan Baskar Ramamoorthy Boomishankar Selvarajan Nagendran 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):699-701
The reactions of n-butyl stannonic acid with(PhO) 2 P(O)H leads to the formation of a hexameric tin cage [{(n-BuSn) 3 (PhO) 3 O} 2 {HPO 3 } 4 ].This reaction involves an in situ P─O bond cleavage and the generation of a [HPO 3 ] 2? ion. A direct reaction of six equivalents of n-BuSnO(OH) acid with six equivalents of C 6 H 5 OH and four equivalents of H 3 PO 3 also leads to the formation of same cage structure. A tetranuclear organooxotin cage[(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] 2 has been assembled by debenzylation involving the reaction of (PhCH 2 ) 2 SnCl 2 ,(PhCH 2 ) 2 SnO·H 2 O or (PhCH 2 ) 3 SnCl with two equivalents of t-BuP(O)OH 2 . A half-cage intermediate [(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] has been detected. New organotin cations of the type [n-Bu 2 Sn(H 2 O) 4 ] 2+[2,5-Me 2 -C 6 H 3 SO 3 ]? 2 and {[n-Bu 2 Sn(H 2 O) 3 LSn(H 2 O) 3 (n-Bu) 2 ] 2+[1,5-(SO 3 ) 2 -C 10 H 6 ] 2?} have been obtained in the reactions of n-Bu 2 SnO or (n-Bu 3 Sn) 3 O with 2,5-dimethyl sulfonic acid and 1,5-naphthalene disulfonic acid respectively. These organotin cations form interesting supramolecular structures in the solid state as a result of O─H─···O hydrogen bonding. 相似文献