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1.
Organotin derivatives of dimethyldithioarsinic (dithocacodylic) acid have been obtained from the appropriate organotin chloride and the sodium salt of the latter. Tin(IV) chloride and NaS 2AsMe 2 · 2 H 2O yielded only two products, namely Cl 2Sn(S 2AsMe 2) 2 and Sn (S 2AsMe 2) 4, regardless of the reagent ratio. Spectroscopic characterization of the compounds (infrared and 1H NMR) provides structural information suggesting that the dimethyldithioarsinato group behaves as monodentate (or anisobidentate) ligand in Me 2Sn(S 2AsMe 2) 2, Bu 2Sn-(S 2AsMe 2) 2 and Cy 3Sn(S 2AsMe 2), as bidentate in Ph 2Sn(S 2AsMe 2) 2, Ph 3Sn(S 2AsMe 2) and Cl 2As(S 2AsMe 2) 2, whereas Sn(S 2AsMe 2) 4 contains both mono- and bidentate ligands, presumably in a six-coordinate structure. 相似文献
2.
The interaction of the clathrate Pt 6Cl 12 · 0.1 EtCl · 5.7H 2O with RCN nitriles results in cis-[Pt(PhCH 2CN) 2Cl 2] and in [Pt(RCN) 2Cl 2] (R = CH 2CO 2Et, Ph) complexes as a mixture of cis- and trans-isomers which separated and characterized. Cis-[Pt(MeCN) 2Cl 2] has been synthesized using a well known technique of K 2[PtCl 4] interaction with acetonitrile in water. Heating cis-[Pt(RCN) 2Cl 2] (R = Me, CH 2Ph, CH 2CO 2Et) in the solid phase leads to cis-trans isomerization. In case of cis-[Pt(PhCN) 2Cl 2] thermal conversion results in trans-[Pt(PhCN) 2Cl 2] but the process of geometrical isomerizations accompained by a considerable decomposition of starting material and/or final products. Boiling of cis-[Pt(PhCH 2CN 2)Cl 2] in mixture of EtNO 2? PhCH 2CN or cis-[Pt(EtCO 2CH 2CN) 2Cl 2] in MeNO 2 or EtNO 2 solutions results in complete cis-trans conversion. Similarily heating of cis-[Pt(RCN) 2Cl 2] (R = Me, Ph) in solution produces an equilibrium mixture of cis- and transisomers. 相似文献
3.
Inhaltsübersicht. Die Verbindungen K 2MnS 2, Rb 2MnS 2, Cs 2MnS 2, K 2MnSe 2, Rb 2MnSe 2, Cs 2MnSe 2, K 2MnTe 2, Rb 2MnTe 2 und Cs 2MnTe 2 wurden durch Umsetzungen von Alkalimetall-carbonaten mit Mangan bzw. Mangantellurid in einem mit Chalkogen beladenen Wasserstoffstrom erhalten. Kristallstrukturuntersuchungen an Einkristallen ergaben, daß alle neun Verbindungen isotyp kristallisieren (K 2ZnO 2-Typ, Raumgruppe Ibam). Untersuchungen zum magnetischen Verhalten zeigen antiferromagnetische Kopplungen der Manganionen in den [MnX 4/22–]-Ketten, On Alkali Metal Manganese Chalcogenides A 2MnX 2 with A K, Rb, or Cs and X S, Se, or Te The compounds K 2MnS 2, Rb 2MnS 2, Cs 2MnS 2, K 2MnSe 2, Rb 2MnSe 2, Cs 2MnSe 2, K 2MnTe 2, Rb 2MnTe 2, and Cs 2MnTe 2 were synthesized by the reaction of alkali metal carbonates with Mn or MnTe in a stream of hydrogen charged with chalcogen. Structural investigations on single crystals show that all nine compounds crystallize in isotypic atomic arrangements (K 2ZnO 2 type, space group Ibam). The magnetic behaviour indicates antiferromagnetic interactions of the manganese ions within the [MnX 1/22–] chains. 相似文献
4.
On the refluxing of M(II) oxalate ( M=Mn, Co, Ni, Cu, Zn or Cd) and 2-ethanolamine in chloroform, the following complexes were obtained: MnC 2O 4·HOCH 2CH 2NH 2·H 2O, CoC 2O 4·2HOCH 2CH 2NH 2, Ni 2(C 2O 4) 2·5HOCH 2CH 2NH 2·3H 2O, Cu 2(C 2O 4) 2·5HOCH 2CH 2NH 2, Zn 2(C 2O 4) 2·5HOCH 2CH 2NH 2·2H 2O and Cd 2(C 2O 4) 2·HOCH 2CH 2NH 2·2H 2O. Following the reaction of M(II) oxalate with 2-ethanolamine in the presence of ethanolammonium oxalate, a compound with the empirical formula ZnC 2O 4·HOCH 2CH 2NH 2·2H 2O 1 was isolated. The complexes were identified by using elemental analysis, X-ray powder diffraction patterns, IR spectra, and thermogravimetric and differential thermal analysis. The IR spectra and X-ray powder diffraction patterns showed that the complexes obtained were not isostructural. Their thermal decompositions, in the temperature interval between 20 and about 900°C, also take place in different ways, mainly through the formation of different amine complexes. The DTA curves exhibit a number of thermal effects. 相似文献
5.
Alloys in the As 2S 3-TlAs 2S 2Se 2 section of the As 2S 3-As 2Se 3-TlS ternary system were studied and a phase diagram was constructed using physicochemical methods (differential thermal analysis,
microstructural analysis, X-ray powder diffraction, also microhardness and density measurements). The diagram in the As 2S 3-TlAs 2S 2Se 2 section is a non-quasi-binary diagonal section of the As 2S 3-As 2Se 3-TlSe quasi-ternary system. It was found that all the alloys in the section under ordinary conditions are obtained in the
vitreous state. At low As 2S 3 concentrations in the section, solid solutions form up to 2.5 mol %, and at low TlAs 2S 2Se 2 concentrations, their extent is 3 mol %. 相似文献
6.
The crystallisation kinetics of experimental glasses in 3 different systems: (A) Li 2O–SiO 2, (B) Li 2O–Al 2O 3–SiO 2 and (C) Li 2O–K 2O–Al 2O 3–SiO 2 were studied under non-isothermal conditions. The DTA results revealed a stronger tendency to crystallisation of binary compositions in comparison to the ternary and quaternary compositions comprising Al 2O 3 and K 2O which present the lower crystallisation, i.e. the crystallisation propensity follows the trend A > B > C. The devitrification process in the Li 2O–SiO 2 and Li 2O–Al 2O 3–SiO 2 systems began earlier and the rate was higher in comparison to that of glasses in the quaternary Li 2O–K 2O–Al 2O 3–SiO 2 system. Thus, addition of Al 2O 3 and K 2O to glasses of Li 2O–SiO 2 system was demonstrated to promote glass stability against crystallisation. However, the activation energy for crystallisation was shown to depend also on the SiO 2/Li 2O ratio with the binary system showing a decreasing trend with increasing SiO 2/Li 2O ratio, while the opposite tendency was being observed for compositions with added Al 2O 3 and K 2O. 相似文献
7.
Various cyclic phosphonium structures are formed in high yield by the deprotection of unstable phosphine-aldehydes in acidic solution. When there is a methylene spacer between the phosphine and the aldehyde, a phosphonium ion [PHR 2CH 2CH(OEt) 2]Br 2, R=iPrOH, Et is obtained. Reaction of these phosphonium salts with water produces the dimers [-PR 2CH 2CH(OH)-] 2[Br] 2 R = iPr, Et. When there is an ethylene spacer as in PPh 2CH 2CH 2CH(OCH 2CH 2O), a remarkable tetramer with a 16-membered ring [-PPh 2CH 2CH 2CH (OH)-] 4[Cl] 4 forms as one diastereomer in hydrochloric acid solution. Reaction of HCl with the protected phosphine-aldehyde with a propylene spacer (PPh 2CH 2CH 2CH 2CH(OCH 2CH 2O)) results in the formation of the monomeric phosphonium salt [-PPh 2 CH 2CH 2CH 2CH(OH)-]Cl with a 5-membered ring. Solid state structures of different ring types were determined using X-ray diffraction experiment. 相似文献
8.
In dissociation experiments of H 2O 2 under shock wave conditions, the spectra of H 2O 2 and HO 2 have been observed in the UV at 2200 ≤ 2800 Å. By the use of these spectra the H 2O 2 decomposition in the presence of H 2 and CO at 870 ≤ T ≤ 1000°K has been analyzed. It was found that in this temperature range, in contrast to low temperature behavior, reactions of H atoms with H 2O 2 and with HO 2 are equally important. The rate of the reaction H + H 2O 2 ← HO 2 + H 2 was estimated in comparison with the rate of the reaction between H and HO 2. Good agreement between calculated and measured concentration profiles of HO 2 and H 2O 2 was obtained. 相似文献
9.
Abstract Reactions of HBr with trans-[W(N 2) 2(dppe)PPh 2Me) 2] (1) (dppe = Ph 2CH 2CH 2PPh 2) result in protonation of coordinated N 2 but no formation of ammonia or hydrazine. The tungsten-containing product depends upon the reaction conditions: (i) in MeOH, the product formed is [WBr(NNH 2) (dppe)(PPh 2Me) 2]HBr 2 (2) which converts to the hydride, [WBr 2(H)(NNH 2(dppe)(PPh 2Me)](Br(3), with loss of phosphine in THF or CH 2Cl 2, (ii) in THF or CH 2Cl 2, the hydride (3) is formed directly. Reaction of 2 with Na 2CO 3 in MeOH results in the loss of HBr and the formation of the diazenido complex [WBr(NNH)(dppe)(PPh 2Me) 2] which reacts further with Na 2CO 3 in benzene under N 2 to lose HBr and form a mixture of 1 and trans-[W(N 2)(dppe) 2]. The reaction of 1 with aqueous HF forms [WF(NNH 2)(dppe)(PPh 2Me) 2]BF 4. The X-ray photoelectron spectra of trans-[M(N 2) 2 (dppe) 2], [MBr(NNH 2)(dppe) 2Br (M = Mo, W), [WCl(NNH 2)(dppe) 2]Cl, [WCl(N)(dppe) 2]Cl and [WCl(NH) (dppe) 2] are reported. In all of these complexes, nitrogen is in a highly reduced form. 相似文献
10.
Syntheses of diols of structure [HOCH 2CH 2S] 2(CH 2) n in 86–95% yield from the sodium salt of 2-mercaptoethanol and Br(CH 2) nBr (n = 1 to 5) or in 60–90% yield from 2-chloroethanol and NaS(CH 2) nSNa (n = 2 to 5) are described. The diol [HOCH 2CH 2SCH 2CH 2] 2O was prepared in 82% yield from the sodium salt of 2-mercaptoethanol and [ClCH 2CH 2] 2O, and in 88% yield from 2-chloroethanol and [HSCH 2CH 2] 2O. Mono- and bis-sulfoxides and bis-sulfones of these species were prepared in generally high yield by treatment with an equivalent of KIO 4 in aqueous methanol, two equivalents of NaIO 4 in aqueous methanol, or four equivalents of H 2O 2 in trifluoroacetic acid respectively. The compounds are important analytical standards for investigating the fate of the chemical warfare agents sesquimustard Q and oxygen mustard T in environmental samples. 相似文献
11.
Alternative Ligands. XXXV. Syntheses of Bidentate P‐Donor/Sn‐Acceptor Ligands: Coordination Experiments with Cp*Rh(CO) 2 and CpRh(C 2H 4) 2 Donor/acceptor ligands Me 2Sn(CH 2CH 2PMe 2) 2 ( 1 ) and Me 2Sn(OCH 2PMe 2) 2 ( 2 ) have been prepared by radical reaction of Me 2PVi with Me 2SnH 2 and by substitution of chlorine in Me 2SnCl 2 or of ethoxy groups in Me 2Sn(OEt) 2 by MOCH 2PMe 2 (M = Li, Na) and HOCH 2PMe 2, respectively. 2 cannot be isolated in pure form from the product mixture because, due to condensation reactions, the “ladder structure” [Me 2Sn(OCH 2PMe 2) 2OSnMe 2] 2 ( 3 ) is formed. The molecular structure of 3 was determined by X‐ray diffraction studies of single crystals. Attempts to produce the thiophosphoryl derivative of 3 result in the degradation of the ladder structure giving the thermally labile phosphane sulfide Me 2Sn(OCH 2P(S)Me 2) 2. Ligands 1 and 2 besides Me 2PCH 2CH 2SnMe 3 ( 4 ) have been used for the preparation of rhodium(I) complexes from Cp*Rh(CO) 2 ( 5 ) or CpRh(C 2H 4) 2 ( 10 ) as educts. The thermal reaction of 5 with 4 yields Cp*Rh(CO)PMe 2CH 2CH 2SnMe 3 ( 6 ), that of 5 with 1 a mixture of the mononuclear derivative Cp*Rh(CO) · PMe 2CH 2CH 2SnMe 2CH 2CH 2PMe 2 ( 7 ) and the binuclear complex [Cp*Rh(CO)PMe 2CH 2CH 2] 2SnMe 2 ( 8 ). The related system [Cp*Rh(CO)PMe 2CH 2O] 2SnMe 2 produced by reaction of 5 with 2 can only be detected in solution but, because of some side‐products, was not fully characterized. From 10 and 4 a mixture of mono‐ and disubstituted products, CpRh(C 2H 4)PMe 2CH 2CH 2SnMe 3 ( 11 ) and CpRh(PMe 2CH 2CH 2SnMe 3) 2 ( 12 ), is obtained. Reaction of 1 with 10 yields a mixture of the complexes CpRh(C 2H 4)PMe 2CH 2CH 2SnMe 2CH 2CH 2PMe 2 ( 13 ) and CpRh(Me 2CH 2CH 2) 2SnMe 2 ( 14 ). Some of the NMR data ( 13C, δδ Sn) of 14 can be interpreted in terms of the expected Rh → Sn interaction. A definite proof by X‐ray diffraction on single crystals, so far, was not possible. 相似文献
12.
Investigation of Cocrystallization in the Systems Mn(OOCCH 3) 2-Co(OOCCH 3) 2-H 2O, Mn(OOCCH 3) 2-Ni(OOCCH 3) 2-H 2O, Mn(OOCCH 3) 2-Zn(OOCCH 3) 2-H 2O at 60°C The three-component systems Mn(OOCCH 3) 2-Co(OOCCH 3) 2-H 2O, Mn(OOCCH 3) 2-Ni(OOCCH 3) 2-H 2O and Mn(OOCCH 3) 2-Zn(OOCCH 3) 2-H 2O at 60°C were investigated by physio-chemical analysis. There is an interruption in the series of mixed crystals formed in the three-component systems. The inclusion of Co 2+- and Ni 2+ in Mn(OOCCH 3) 2 · 2 H 2O of Mn 2+ in Co(OOCCH 3) 2 · 2 H 2O, Zn(OOCCH 3) 2 · 2 H 2O and Ni(OOCCH 3) 2 · 4 H 2O is based on isodimorphic substitution. It was found that in the system Mn(OOCCH 3) 2-Zn(OOCCH 3) 2-H 2O crystallizes Zn(OOCCH 3) 2 · Mn(OOCCH 3) 2 · 2 H 2O. It was identified by the X-ray and differential thermal analysis. 相似文献
13.
Abstract The reaction of Me 2PO 2H and Me 2AsO 2H with SbCl 3, BiCl 3, and Bi(NO 3) 3·5H 2O gave the complexes Sb(Me 2PO 2) 3, Sb(Me 2AsO 2) 3, (Me 2PO 2) 2Bi-Cl, Bi(Me 2AsO 2) 3, (Me 2PO 2) 2Bi(NO 3), and (Me 2AsO 2) 2Bi(NO 3)·H 2O, respectively. The arsinato complexes did not react with the Lewis bases pyridine, Ph 3P, and Ph 3As in acetone. The compounds Sb(Me 2AsO 2) 3 and (Me 2AsO 2) 2Bi(NO 3)·H 2O reacted to a small extent with nicotinic acid in methanol but Bi(Me 2AsO 2) 3 gave (Me 2AsO 2-BiO) x in good yields. (Me 2AsO 2) 2Bi(NO 3)·H 2O in methanol quantitatively rearranged to new complexes with the same composition, [(Me 2AsO 2) 2Bi(NO 3)·H 2O]′ and [(Me 2AsO 2) 2Bi(NO 3)·H 2O]″ in the presence of pyridine. With thiophenol in air, Sb(Me 2AsO 2) 3 gave PhSSPh and Me 2As-SPh (1:1 mol ratio), (Me 2AsO 2-SbO) x and some Sb(Me 2AsO 2) 3 was reformed, Bi(Me 2AsO 2) 3 gave (Me 2AsO 2-BiO) x , PhSSPh, and Me 2As-SPh (1:0.6 mol ratio), whereas (Me 2AsO 2) 2Bi(NO 3)·H 2O quantitatively gave PhSSPh, thus acting as a catalyst for the air oxidation of thiophenol. 相似文献
14.
Phase ratios in the three-component oxide system K 2O-V 2O 4-SO 3 in the region of the sulfur trioxide concentrations corresponding to its concentrations in the active component of vanadium catalysts for SO 2 to SO 3 conversion have been studied using powder X-ray diffraction, IR spectroscopy, microscopy, and chemical analysis. Four individual compounds (K 2VO(SO 4) 2, K 2(VO) 2(SO 4) 3, K 2VO(SO 4) 2S 2O 7, and K 2(VO) 2(SO 4) 2S 2O 7) and K 2(VO) 2(SO 4) 2S 2O 7 and VOSO 4-base solid solutions of composition K 2(VO) 2+x (SO 4) 2+x S 2O 7 (0 ≤ x ≤ 1.5) were found in the system. K 2VO(SO 4)S 2O 7 and K 2(VO) 2(SO 4) 2S 2O 7 lose their sulfur trioxide when heated above 350°C under an inert atmosphere, and convert to K 2VO(SO 4) 2 and K 2(VO) 2(SO 4) 3, respectively. This implies that K 2VO(SO 4) 2S 2O 7 and K 2(VO) 2(SO 4) 2S 2O 7, as well as K 2(VO) 2+x (SO 4) 2+x S 2O 7 solid solution, cannot exist in the active component of real industrial catalysts. 相似文献
15.
Reactive species generated in the gas and in water by cold air plasma of the transient spark discharge in various N2/O2 gas mixtures (including pure N2 and pure O2) have been examined. The discharge was operated without/with circulated water driven down the inclined grounded electrode. Without water, NO and NO2 are typically produced with maximum concentrations at 50% O2. N2O was also present for low O2 contents (up to 20%), while O3 was generated only in pure O2. With water, gaseous NO and NO2 concentrations were lower, N2O was completely suppressed and HNO2 increased; and O3 was lowered in O2 gas. All species production decreased with the gas flow rate increasing from 0.5 to 2.2 L/min. Liquid phase species (H2O2, NO2 ̄, NO3 ̄, ·OH) were detected in plasma treated water. H2O2 reached the highest concentrations in pure N2 and O2. On the other hand, nitrites NO2 ̄ and nitrates NO3 ̄ peaked between 20 and 80% O2 and were associated with pH reduction. The concentrations of all species increased with the plasma treatment time. Aqueous ·OH radicals were analyzed by terephthalic acid fluorescence and their concentration correlated with H2O2. The antibacterial efficacy of the transient spark on bacteria in water increased with water treatment time and was found the strongest in the air-like mixture thanks to the peroxynitrite formation. Yet, significant antibacterial effects were found even in pure N2 and in pure O2 most likely due to high ·OH radical concentrations. Controlling the N2/O2 ratio in the gas mixture, gas flow rate, and water treatment time enables tuning the antibacterial efficacy. 相似文献
16.
Chemical Vapor Transport of Solid Solutions. 23 Chemical Vapor Transport of Mixed Phases in the System MoS 2/MoSe 2, MoS 2/NbS 2, MoSe 2/NbSe 2 and NbS 2/NbSe 2 X‐ray powder investigations have shown that MoS 2/MoSe 2, MoS 2/NbS 2, MoSe 2/NbSe 2 and NbS 2/NbSe 2 form mixed crystals without a miscibility gap. The mixed crystals can be prepared by heating the Elements for some days in the presence of small amounts of iodine as well as by chemical vapour transport. In the systems NbS 2/NbSe 2 and MoS 2/MoSe 2 the vapor transport occurs congruently, in the systems NbS 2/MoS 2 and NbSe 2/MoSe 2 however a strong enrichment of Niobium has been observed during the transport process. Mass spectrometric investigations and thermochemical calculations have shown that the transport occurs via NbI 4(g) and MoI 3(g). 相似文献
17.
(NEt 4) 2[W IVO(S 2C 2(CN) 2) 2] ( 1), isolated by reaction of Na 2 WO 4, Na 2S 2C 2(CN) 2 (Na 2mnt) in acidified (pH5.5) aqueous medium in the presence of excess of sodium dithionite and NEt 4Br, reduces CO 2/HCO
3
−
(pH 7.5) to yield HCOO − and (NEt 4) 2[W VIO 2(S 2C 2(CN) 2) 2] (2) mimicking tungsten-formate dehydrogenase (W-FDH) activity. ( 1) reacts with Na 2MoO 4 in acidic medium to produce [Mo IvO(S 2C 2(CN) 2) 2] 2− implicating the displacement of tungsten by molybdenum from the cofactor complex in W-FDH. 相似文献
18.
An aqueous solution of (hydroxymethyl)triphosphine [(HOCH 2) 2P(CH 2) 2] 2PCH 2OH ( II) was synthesized in situ by treatment of the triphosphine H 2P(CH 2) 2PH(CH 2) 2PH 2 with formaldehyde. Addition of a CH 2Cl 2 solution of trans-PdCl 2(PhCN) 2 to an in situ aqueous solution of II resulted in the formation of a species thought to be [PdCl{[(HOCH 2) 2P(CH 2) 2] 2PCH 2OH}] +Cl −. Attempts to isolate the complex were unsuccessful because of conversion to material containing small amounts of phosphine
oxide(s) formed via a redox reaction involving water. The triphosphine trioxide [(HOCH 2) 2P(O)(CH 2) 2] 2P(O)CH 2OH was readily isolated from an in situ solution of II by treatment with aqueous H 2O 2. 相似文献
19.
Three diiron and tetrairon azadithiolate complexes as models for the active site of [FeFe] hydrogenase were prepared. Reaction of complex Fe 2(SCH 2OH) 2(CO) 6 and NH 2CH 2CH 2CH 2OCH 3 resulted in the diiron azadithiolate hexcarbonyl complex Fe 2[(SCH 2) 2NCH 2CH 2CH 2OCH 3](CO) 6 ( 1 ) in moderate yield. Furthermore, treatment of complex 1 with mono phosphine ligand PPh 3 and diphosphine ligand Ph 2PCH 2CH 2PPh 2 in the presence of decarbonylation reagent Me 3NO · 2H 2O yielded the phosphine‐substituted azadithiolate complexes Fe 2[(SCH 2) 2NCH 2CH 2CH 2OCH 3]CO) 5(PPh 3) ( 2 ) and {Fe 2[(SCH 2) 2NCH 2CH 2CH 2OCH 3](CO) 5} 2(Ph 2PCH 2CH 2PPh 2) ( 3 ) respectively. The new complexes 1 – 3 were fully characterized by elemental analysis, IR, 1H, 13C, 31P NMR spectroscopy and X‐ray crystallography. It is worthy to note that the crystallographic studies show the unusual difference of the methoxypropanyl substituent on the N atom of complexes 1 and 2 , largely because of the affection of phosphine ligand PPh 3. In addition, complex 1 was found to be a catalyst for H 2 production under electrochemical condition. 相似文献
20.
Preparation and Crystal Structure of SrCu 2Sb 2 and SrZnBi 2 SrCu 2Sb 2 and SrZnBi 2 have been prepared and analytically and structurally characterized. SrCu 2Sb 2 crystallizes tetragonal in the CaBe 2Ge 2 structure type. SrZnBi 2 has its own structure type. In both structures the transition metal atoms form with the semimetal atoms tetragonal pyramids, which are connected by common edges of the basis to twodimensional sheets. These sheets are separated in the case of SrCu 2Sb 2 by single sheets of strontium atoms, in the case of SrZnBi 2 by double sheets of strontium atoms in which fourfold nets of Bi atoms are located. 相似文献
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