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1.
The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe2: [(PbSe)1.14]4[NbSe2]4, [(PbSe)1.14]3[NbSe2]3[(PbSe)1.14]1[NbSe2]1, [(PbSe)1.14]3[NbSe2]2[(PbSe)1.14]1[NbSe2]2, [(PbSe)1.14]2[NbSe2]3[(PbSe)1.14]2[NbSe2]1, [(PbSe)1.14]2[NbSe2]2[(PbSe)1.14]1[NbSe2]1[(PbSe)1.14]1[NbSe2]1, [(PbSe)1.14]2[NbSe2]1[(PbSe)1.14]1[NbSe2]2[(PbSe)1.14]1[NbSe2]1. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.  相似文献   

2.
The reaction of o-C6H4(AsMe2)2 with VCl4 in anhydrous CCl4 produces orange eight-coordinate [VCl4{o-C6H4(AsMe2)2}2], whilst in CH2Cl2 the product is the brown, six-coordinate [VCl4{o-C6H4(AsMe2)2}]. In dilute CH2Cl2 solution slow decomposition occurs to form the VIII complex [V2Cl6{o-C6H4(AsMe2)2}2]. Six-coordination is also found in [VCl4{MeC(CH2AsMe2)3}] and [VCl4{Et3As)2]. Hydrolysis of these complexes occurs readily to form vanadyl (VO2+) species, pure samples of which are obtained by reaction of [VOCl2(thf)2(H2O)] with the arsines to form green [VOCl2{o-C6H4(AsMe2)2}], [VOCl2{MeC(CH2AsMe2)3}(H2O)] and [VOCl2(Et3As)2]. Green [VOCl2(o-C6H4(PMe2)2}] is formed from [VOCl2(thf)2(H2O)] and the ligand. The [VOCl2{o-C6H4(PMe2)2}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C6H4(P(O)Me2)2}2(H2O)]Cl2, but in contrast, the products formed from similar treatment of [VCl4{o-C6H4(AsMe2)2}x] or [VOCl2{o-C6H4(AsMe2)2}] contain the novel arsenic(V) cation [o-C6H4(AsMe2Cl)(μ-O)(AsMe2)]+. X-ray crystal structures are reported for [V2Cl6{o-C6H4(AsMe2)2}2], [VO(H2O){o-C6H4(P(O)Me2)2}2]Cl2, [o-C6H4(AsMe2Cl)(μ-O)(AsMe2)]Cl·[VO(H2O)3Cl2] and powder neutron diffraction data for [VCl4{o-C6H4(AsMe2)2}2].  相似文献   

3.
The photochemical reaction of piperazine with C70 produces a mono‐adduct (N(CH2CH2)2NC70) in high yield (67 %) along with three bis‐adducts. These piperazine adducts can combine with various Lewis acids to form crystalline supramolecular aggregates suitable for X‐ray diffraction. The structure of the mono‐adduct was determined from examination of the adduct I2N(CH2CH2)2NI2C70 that was formed by reaction of N(CH2CH2)2NC70 with I2. Crystals of polymeric {Rh2(O2CCF3)4N(CH2CH2)2NC70}n?nC6H6 that formed from reaction of the mono‐adduct with Rh2(O2CCF3)4 contain a sinusoidal strand of alternating molecules of N(CH2CH2)2NC70 and Rh2(O2CCF3)4 connected through Rh?N bonds. Silver nitrate reacts with N(CH2CH2)2NC70 to form black crystals of {(Ag(NO3))4(N(CH2CH2)2NC70)4}n?7nCH2Cl2 that contain parallel, nearly linear chains of alternating (N(CH2CH2)2NC70 molecules and silver ions. Four of these {Ag(NO3)N(CH2CH2)2NC70}n chains adopt a structure that resembles a columnar micelle with the ionic silver nitrate portion in the center and the nearly non‐polar C70 cages encircling that core. Of the three bis‐adducts, one was definitively identified through crystallization in the presence of I2 as 12{N(CH2CH2)2N}2C70 with addends on opposite poles of the C70 cage and a structure with C2v symmetry. In 12{I2N(CH2CH2)2N}2C70, individual 12{I2N(CH2CH2)2N}2C70 units are further connected by secondary I2???N2 interactions to form chains that occur in layers within the crystal. Halogen bond formation between a Lewis base such as a tertiary amine and I2 is suggested as a method to produce ordered crystals with complex supramolecular structures from substances that are otherwise difficult to crystallize.  相似文献   

4.
Hydrolysis reactions of di- and trinuclear organotin halides yielded large novel cage compounds containing Sn−O−Sn bridges. The molecular structures of two octanuclear tetraorganodistannoxanes showing double-ladder motifs, viz., [{Me3SiCH2(Cl)SnCH2YCH2Sn(OH)CH2SiMe3}2(μ-O)2]2 [ 1 , Y=p-(Me)2SiC6H4-C6H4Si(Me)2] and [{Me3SiCH2(I)SnCH2YCH2Sn(OH)CH2SiMe3}2(μ-O)2]2 ⋅ 0.48 I2 [ 2⋅ 0.48 I2, Y=p-(Me)2SiC6H4-C6H4Si(Me)2], and the hexanuclear cage-compound 1,3,6-C6H3(p-C6H4Si(Me)2CH2Sn(R)2OSn(R)2CH2Si(Me)2C6H4-p)3C6H3-1,3,6 ( 3 , R=CH2SiMe3) are reported. Of these, the co-crystal 2⋅ 0.48 I2 exhibits the largest spacing of 16.7 Å reported to date for distannoxane-based double ladders. DFT calculations for the hexanuclear cage and a related octanuclear congener accompany the experimental work.  相似文献   

5.
The acid–base reaction between Y(CH2SiMe3)3(thf)2 and the pyridyl‐functionalized cyclopentadienyl (Cp) ligand C5Me4H? C5H4N (1 equiv) at 0 °C afforded a mixture of two products: (η5:κ‐C5Me4? C5H4N)Y(CH2SiMe3)2(thf) ( 1 a ) and (η5:κ‐C5Me4? C5H4N)2YCH2SiMe3 ( 1 b ), in a 5:2 ratio. Addition of the same ligand (2 equiv) to Y(CH2SiMe3)3(thf)2, however, generated 1 b together with the novel complex 1 c , the first well defined yttrium mono(alkyl) complex (η5:κ‐C5Me4? C5H4N)[C5HMe3(η3‐CH2)‐C5H4N‐κ]Y(CH2SiMe3) containing a rare κ/η3‐allylic coordination mode in which the C? H bond activation occurs unexpectedly with the allylic methyl group rather than conventionally on Cp ring. If the central metal was changed to lutetium, the equimolar reaction between Lu(CH2SiMe3)3(thf)2 and C5Me4H? C5H4N exclusively afforded the bis(alkyl) product (η5:κ‐C5Me4? C5H4N)Lu(CH2SiMe3)2(thf) ( 2 a ). Similarly, the reaction between the ligand (2 equiv) and Lu(CH2SiMe3)3(thf)2 gave the mono(alkyl) complex (η5:κ‐C5Me4? C5H4N)2LuCH2SiMe3 ( 2 b ), in which no ligand redistribution was observed. Strikingly, treatment of Sc(CH2SiMe3)3(thf)2 with C5Me4H? C5H4N in either 1:1 or 1:2 ratio at 0 °C generated the first cyclopentadienide‐based scandium zwitterionic “tuck‐over” complex 3 , (η5:κ‐C5Me4? C5H4N)Sc(thf)[μ‐η5:η1:κ‐C5Me3(CH2)‐C5H4N]Sc(CH2SiMe3)3. In the zwitterion, the dianionic ligand [C5Me3(CH2)‐C5H4N]2? binds both to Sc13+ and to Sc23+, in η5 and η1/κ modes. In addition, the reaction chemistry, the molecular structures, and the mechanism are also discussed in detail.  相似文献   

6.
Phase relations have been established in the ternary system Ce-Rh-Si for the isothermal section at 800 °C based on X-ray powder diffraction and EPMA on about 80 alloys, which were prepared by arc melting under argon or by powder reaction sintering. From the 25 ternary compounds observed at 800 °C 13 phases have been reported earlier. Based on XPD Rietveld refinements the crystal structures for 9 new ternary phases were assigned to known structure types. Structural chemistry of these compounds follows the characteristics already outlined for their prototype structures: τ7—Ce3RhSi3, (Ba3Al2Ge2-type), τ8—Ce2Rh3−xSi3+x (Ce2Rh1.35Ge4.65-type), τ10—Ce3Rh4−xSi4+x (U3Ni4Si4-type), τ11—CeRh6Si4 (LiCo6P4-type), τ13—Ce6Rh30Si19.3 (U6Co30Si19-type), τ18—Ce4Rh4Si3 (Sm4Pd4Si3-type), τ21—CeRh2Si (CeIr2Si-type), τ22—Ce2Rh3+xSi1−x (Y2Rh3Ge-type) and τ24—Ce8(Rh1−xSix)24Si (Ce8Pd24Sb-type). For τ25—Ce4(Rh1−xSix)12Si a novel bcc structure was proposed from Rietveld analysis. Detailed crystal structure data were derived for τ3—CeRhSi2 (CeNiSi2-type) and τ6—Ce2Rh3Si5 (U2Co3Si5-type) by X-ray single crystal experiments, confirming the structure types. The crystal structures of τ4—Ce22Rh22Si56, τ5—Ce20Rh27Si53 and τ23—Ce33.3Rh58.2−55.2Si8.5−11.5 are unknown. High temperature compounds with compositions Ce10Rh51Si33 (U10Co51Si33-type) and CeRhSi (LaIrSi-type) have been observed in as-cast alloys but these phases do not participate in the phase equilibria at 800 °C.  相似文献   

7.
Photoirradiation of Os3(CO)10(C14H20) (1) in n-hexane produces the double-decker cluster [Os3(CO)9(C28H40)] [Os3(CO)10] (7), which can also be prepared from the reaction of Os3(CO)9(C28H40) (2) and Os3(CO)10(NCMe)2. Further reaction of 7 with Os3(CO)10(NCMe)2 affords the triple-decker cluster [Os3(CO)9(C28H40)][Os3(CO)10]2 (8). The bis(diyne) complex Os3(CO)8(C14H20)2 (3) reacts with Os3(CO)10(NCMe)2 sequentially to yield the double-decker cluster [Os3(CO)8(C14H20)2][Os3(CO)10] (4) and the triple-decker cluster [Os3(CO)8(C14H20)2][Os3(CO)10]2 (5). Treatment of 3 with Co2(CO)8 at room temperature leads to the mixed-metal triple-decker cluster [Os3(CO)8(C14H20)2][Co2(CO)6]2 (6), while the reaction of 2 and Co2(CO)8 produces [Os3(CO)9(C28H40)][Co2(CO)6]2 (9) and [Os2(CO)6(C28H40)][Co2(CO)6]2 (10). Compound 10, which involves cluster degradation from Os3 to Os2, has been structurally characterized by an X-ray diffraction study.  相似文献   

8.
Chloroselenates with Di- and Tetravalent Selenium: 77Se-NMR-Spectra, Syntheses, and Crystal Structures of (PPh4)2SeCl6 · 2 CH2Cl2, (NMe3Ph)2SeCl6, (K-18-crown-6)2SeCl6 · 2 CH3CN, PPh4Se2Cl9, (NEt4)2Se2Cl10, (PPh4)2Se3Cl8 · CH2Cl2, and (PPh4)2Se4Cl12 · CH2Cl2 The title compounds were obtained from reactions of selenium and selenium tetrachloride with PPh4Cl, NEt4Cl, NMe3PhCl, or (K-18-crown-6)Cl in dichloromethane or acetonitrile. (PPh4)2Se3Cl8 · CH2Cl2 was also formed from GeSe, PPh4Cl and chlorine in acetonitrile. The 77Se-NMR spectra of the solutions show the presence of dynamical equilibria which, depending on composition, mainly contain SeCl2, SeCl4, Se2Cl2, SeCl62–, Se2Cl62–, and/or Se2Cl102–. Solutions of AsCl3 and (PPh4)2Se4 in acetonitrile upon chlorination with Cl2 or PPh4AsCl6 yielded (PPh4)2Se2Cl6, while (PPh4)2As2Se4Cl12 was the product after chlorination with SOCl2. According to the X-ray crystal structure analyses the ions SeCl62–, Se2Cl9–, and Se2Cl102– have the known structures with octahedral coordination of the Se atoms. The structure of the Se3Cl82– ion corresponds to that of Se3Br82– consisting of three SeCl2 molecules associated via two Cl– ions. (PPh4)2Se4Cl12 · CH2Cl2 is isotypic with the corresponding bromoselenate and contains anions in which three SeCl2 molecules are attached to a SeCl62– ion; there is a peculiar Se–Se interaction.  相似文献   

9.
Seven new mixed oxochalcogenate compounds in the systems MII/XVI/TeIV/O/(H), (MII = Ca, Cd, Sr; XVI = S, Se) were obtained under hydrothermal conditions (210 °C, one week). Crystal structure determinations based on single‐crystal X‐ray diffraction data revealed the compositions Ca3(SeO4)(TeO3)2, Ca3(SeO4)(Te3O8), Cd3(SeO4)(Te3O8), Cd3(H2O)(SO4)(Te3O8), Cd4(SO4)(TeO3)3, Cd5(SO4)2(TeO3)2(OH)2, and Sr3(H2O)2(SeO4)(TeO3)2 for these phases. Peculiar features of the crystal structures of Ca3(SeO4)(TeO3)2, Ca3(SeO4)(Te3O8), Cd3(SeO4)(Te3O8), Cd3(H2O)(SO4)(Te3O8), and Sr3(H2O)2(SeO4)(TeO3)2 are metal‐oxotellurate(IV) layers connected by bridging XO4 tetrahedra and/or by hydrogen‐bonding interactions involving hydroxyl or water groups, whereas Cd4(SO4)(TeO3)3 and Cd5(SO4)2(TeO3)2(OH)2 crystallize as framework structures. Common to all crystal structures is the stereoactivity of the TeIV electron lone pair for each oxotellurate(IV) unit, pointing either into the inter‐layer space, or into channels and cavities in the crystal structures.  相似文献   

10.
Reactions of R4Sb2 (R = Me, Et) with (Me3SiCH2)3M (M = Ga, In) and Crystal Structures of [(Me3SiCH2)2InSbMe2]3 and [(Me3SiCH2)2GaOSbEt2]2 The reaction of (Me3SiCH2)3In with Me2SbSbMe2 gives [(Me3SiCH2)2InSbMe2]3 ( 1 ) and Me3SiCH2SbMe2. [(Me3SiCH2)2GaOSbEt2]2 ( 2 ) is formed by the reaction of (Me3SiCH2)3Ga with Et2SbSbEt2 and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.  相似文献   

11.
Syntheses and Crystal Structures of Novel Heterobimetallic Tantalum Coin Metal Chalcogenido Clusters In the presence of phosphine the thiotantalats (Et4N)4[Ta6S17] · 3MeCN reacts with copper to give a number of new heterobimetallic tantalum copper chalcogenide clusters. These clusters show metal chalcogenide units some of which here already known from the chemistry of vanadium and niobium. New Ta—M‐chalcogenide clusters could also be synthesised by reaction of TaCl5 and silylated chalcogen reagents with copper or silver salts in presence of phosphine. Such examples are: [Ta2Cu2S4Cl2(PMe3)6] · DMF ( 1 ), (Et4N)[Ta3Cu5S8Cl5(PMe3)6] · 2MeCN ( 2 ), (Et4N)[Ta9Cu10S24Cl8(PMe3)14] · 2MeCN ( 3 ), [Ta4Cu12Cl8S12(PMe3)12] ( 4 ), (Et4N)[Ta2Cu6S6Cl5(PPh3)6] · 5MeCN ( 5 ), (Et4N)[Ta2Cu6S6Cl5(PPh2Me)6] · 2MeCN ( 6 ), (Et4N)[Ta2Cu6S6Cl5(PtBu2Cl)6] · MeCN ( 7 ) [Ta2Cu2S4Br4(PPh3)2(MeCN)2] · MeCN ( 8 ), [Cu(PMe3)4]2[Ta2Cu6S6(SCN)6(PMe3)6] · 4MeCN ( 9 ), [TaCu5S4Cl2(dppm)4] · DMF ( 10 ), [Ta2Cu2Se4(SCN)2(PMe3)6] ( 11 ), [Cu(PMe3)4]2[Ta2Cu6Se6(SCN)6(PMe3)6] · 4MeCN ( 12 ), [TaCu4Se4(PnPr3)6][TaCl6] ( 13 ), [Ta2Ag2Se4Cl2(PMe3)6] · MeCN ( 14 ), ∞[TaAg3Se4(PMe3)3] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis.  相似文献   

12.
Ten organotin derivatives with dithiocarbamates of the formulae (4‐NCC6H4CH2)2Sn(S2CNEt2)2 (1), (4‐NCC6H4CH2)2Sn(S2CNBz2)2 (2), (4‐NCC6H4CH2)2Sn[S2CN(CH2CH2)2NCH3]2 (3), (2‐ClC6H4CH2)2 Sn(S2CNEt2)2 (4), (2‐ClC6H4CH2)2Sn(S2CNBz2)2 (5), (4‐NCC6H4CH2)2Sn(Cl)S2CNEt2 (6), (4‐NCC6H4CH2)2Sn(Cl)S2CNBz2 (7), (4‐NCC6H4CH2)2Sn(Cl)S2CN(CH2CH2)2NCH3 (8), (2‐ClC6H4CH2)2 Sn(Cl)S2CNEt2 (9) and (2‐ClC6H4CH2)2Sn(Cl)S2CNBz2 (10) have been prepared. All complexes were characterized by elemental analyses, IR and NMR. The crystal structures of complexes 1 and 10 were determined by X‐ray single crystal diffraction. For complex 1, the central tin atom exists in a skew‐trapezoidal planar geometry defined by two asymmetrically coordinated dithiocarbamate ligands and two 4‐cyanobenzyl groups. In addition, because of the presence of close intermolecular non‐bonded contacts, complex 1 is a weakly‐bridged dimer. In complex 10, the central tin atom is rendered pentacoordinated in a distorted trigonal bipyramidal configuration by coordinating with S atoms derived from the dithiocarbamate ligand. In vitro assays for cytotoxicity against five human tumor cell lines (MCF‐7, EVSA‐T, WiDr, IGROV and M226) furnished the significant toxicities of the title complexes. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

13.
Most compounds designed for immobilization in fluorous media feature linear pony tails of the formula (CH2)m(CF2)n−1CF3 [(CH2)mRfn]. This paper presents a first-generation approach to compounds with branched or “split” pony tails of the formula (CH2)lCH[(CH2)mRfn]2. Allyl tri(n-butyl)tin is reacted twice with perfluorooctyl iodide (Rf8I; first, photochemical, 78-81%; second, thermal with radical initiator, 71%; 13-18 g scales) to give the secondary alkyl iodide ICH(CH2Rf8)2 (3). A subsequent Ni(Cl)2(PPh3)2-catalyzed reaction with allyl tri(n-butyl)tin yields the branched alkene H2CCHCH2CH(CH2Rf8)2 (74%). A palladium-catalyzed Heck coupling with OP(p-C6H4Br)3 gives the fluorous phosphine oxide OP(p-C6H4CHCHCH2CH(CH2Rf8)2)3 (84%), and Pd/C-catalyzed hydrogenation affords OP(p-C6H4(CH2)3CH(CH2Rf8)2)3 (>99%). Reduction with SiHCl3 gives P(p-C6H4(CH2)3CH(CH2Rf8)2)3, which is protected as the air-stable borane adduct H3B·P(p-C6H4(CH2)3CH(CH2Rf8)2)3 (9, 64%). The CF3C6F11/toluene partition coefficient of 9 is much higher than that of the analog with p-(CH2)3Rf8 groups (96.6:3.4 versus 37.3:62.7). The iodide 3 is unreactive towards PAr3 at 175-250 °C. However, a CuBr-catalyzed reaction with C6H5MgBr gives C6H5CH(CH2Rf8)2, which also exhibits a high partition coefficient (97.9:2.1).  相似文献   

14.
Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2− were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X‐ray crystal structures.  相似文献   

15.
Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN.  相似文献   

16.
The [((C6H5)3P)2N]+, [(C6H5)4P]+ and [N(CH3)4]+ salts of SeF5−, SeF62− and SeOF3− and CsSeO2F were prepared and characterized. Crystal structures were obtained for [((C6H5)3P)2N][SeF5] and [((C6H5)3P)2N][SeOF3] CH2Cl2. In contrast to oxygen-bridged dimeric TeOF3−, the SeOF3− anion in [((C6H5)3P)2N][SeOF3] CH2Cl2 is monomeric and represents the first experimentally well determined molecular structure of a monomeric trifluoro-chalcogenite anion. Similarly, [((C6H5)3P)2N][SeF5] represents the first example of a structure containing a well-isolated undistorted SeF5− anion. The NMR and the vibrational spectra and their assignments were re-examined and corrected by comparison with high-level theoretical calculations. Whereas the previously published normal coordinate analysis of SeF5− is correct, that for SeOF3− needs major revision.  相似文献   

17.
The Courses of the Ammonolyses of the Ammonium Hexafluorometalates of Aluminum, Gallium, and Indium, (NH4)3MF6 (M = Al, Ga, In) The courses of the ammonolysis reactions of the ammonium hexafluorometalates (NH4)3MF6 (M = Al, Ga, In) were investigated with the aid of in‐situ powder diffractometry and differential thermal analysis. Under these conditions, the reaction of (NH4)3AlF6 with gaseous ammonia yields at about 360 °C AlF3 via the intermediates NH4AlF4, Al(NH3)2F3 and Al(NH3)F3. The ammonolysis of (NH4)3GaF6 produces GaN at about 400 °C. Depending upon the actual reaction conditions, the intermediates NH4GaF4 and Ga(NH3)F3 as well as their ammonia adducts NH4GaF4 · NH3 and Ga(NH3)2F3 and the amide‐ammoniate Ga(NH3)(NH2)F2 are observed. In the case of (NH4)3InF6 the intermediates (NH4)3InF6 · NH3 and In(NH3)F3 may exist; there are also indications for the reduction of In(III) to In(I) and for the existence of In(NH3)2F and InF as products of the ammonolysis of (NH4)3InF6.  相似文献   

18.
Syntheses and Thermal Properties of Cluster Molecules, formed from Groups 11‐13‐16 Elements In the presence of PPh3, CuX (X = Cl, CH3COO) or AgOC(O)C6H5 and GaCl3 react in THF with S(SiMe3)2 or Se(SiMe3)2 to yield [Cu6Ga8Cl4S13(PPh3)6] ( 1 ), [Cu6Ga8Cl4Se13(PPh3)6] ( 2 ), [Ag6Ga8Cl4S13(PPh3)6] ( 4 ) and [Ag6Ga8Cl4Se13(PPh3)6] ( 5 ). The use of PnPr2Ph instead of PPh3 and subsequent layering with n‐hexane leads to the formation of the cluster [Cu6Ga8Cl4Se13(PnPr2Ph)12] ( 3a , 3b ). Reaction of CuCl, GaCl3 and PnPr3 with Se(SiMe3)2 in THF results in the crystallisation of the ionic cluster (HPnPr3)2[Cu2Ga4Cl4Se6(PnPr3)4] ( 6 ). The structures of 1 — 6 were determined by X‐ray single crystal structure analysis. Thermogravimetric measurements of the cluster molecules and powder diffraction patterns of the remaining powders reveal the potential use of them as single source precursor compounds for the synthesis of the related ternary solid state materials.  相似文献   

19.
Reaction of [M(NH3)6]Cl3 (M = Co, Rh, Ir) and [Ir(NH3)5(OH2)]Cl3 with (NH4)2C2O4 · H2O in aqueous solution resulted in the isolation of [M(NH3)6]2(C2O4)3 · 4 H2O and [Ir(NH3)5(OH2)]2(C2O4)3 · 4 H2O, respectively. The complexes have been characterized by X‐ray crystallography, IR and UV/VIS spectroscopy. The isomorphous compounds crystallize in the orthorhombic space group Pnnm (No. 58). Four molecules of crystal water are involved in an extended three‐dimensional hydrogen bonding network. The librational modes of the lattice water around 600 cm–1 allow the characterization of [Ir(NH3)6]2(C2O4)3 · 4 H2O and [Ir(NH3)5(OH2)]2(C2O4)3 · 4 H2O, respectively, by IR spectroscopy. The band around 600 cm–1 shows a significant frequency shift in the IR spectra of the hexaammine and aquapentaammine complex of iridium(III) and, by that, a distinction is possible.  相似文献   

20.
The cloud points (CPs) of the copolymers 17R4 and L64 were first measured, and then the effects of salts ((NH4)3C6H5O7, K3C6H5O7) on 17R4 and L64 were researched. After finishing the work described above, the temperature (278.15, 283.15, and 288.15) K of aqueous two-phase systems was determined, which consist of 17R4-(NH4)3C6H5O7, 17R4-K3C6H5O7, L64-(NH4)3C6H5O7, and L64-K3C6H5O7. Finally, the liquid–liquid equilibrium (LLE) data of binodal curve and the tie line for 17R4-(NH4)3C6H5O7 aqueous two- phase systems (ATPSs) 17R4-K3C6H5O7 ATPSs, L64-(NH4)3C6H5O7 ATPSs, and L64-K3C6H5O7 ATPSs were obtained. Nonlinear fitting of the empirical equation was used for making the diagram. The results showed that the change in the size of the two-phase areas increases with the increase of temperature. The capacity of the salts to induce phase segregation follows the Hofmeister series, that is, K3C6H5O7?>?(NH4)3C6H5O7. In addition, the findings also showed that the phase separation ability of 17R4 is better than that of L64.  相似文献   

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