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1.
《Mendeleev Communications》2021,31(5):631-634
The reactions of imino phenols 3,5-But2-2-HOC6H2CH=NX (X = 8-C9H6N, 2-MeO-5-MeC6H3 and 2-PhOC6H4) with Sc(CH2SiMe3)3(THF)2 in toluene proceed with silane elimination and reductive alkylation of the CN group affording dimeric base-free monoalkyl scandium complexes. X-ray analysis of the two complexes revealed their dimeric structures due to μ-bridging amidophenolato dianions. The complexes catalyze hydrophosphination of styrene, phenylacetylene and tolane with Ph2PH as well as dehydrogenative coupling of anisole with hydrosilanes.  相似文献   

2.
Triorganotin compounds, R3SnX, have found extensive use as a biological agents in such areas as agrochemicals, marine antifoulants and timber preservatives. In contrast, di(R2SnX2) and tetraorganotin derivatives (R4Sn) possess less biological activity than do their triorganotin counterparts. It has been shown that disproportionation of R3SnX species (i.e. to produce R2SnX2 and R4Sn) can occur especially when X is a chelating or bridging group such as oxide, carboxylate, hydroxy ketone or hydroxyquinoline. This process has implications for the industrial applications and analysis of R3SnX compounds.  相似文献   

3.
Principal results and trends in chemistry of organic derivatives of divalent silicon, germanium, and tin containing bonds between these elements and the halogen, nitrogen, oxygen, and sulfur atoms are briefly surveyed. Selected characteristics of compounds with the element--phosphorus and element--arsenic bonds are discussed for comparison. Data on the synthesis and structures of new types of these compounds, viz., germanium(ii) diacylates, the alkoxy derivatives E14(OR)2 and E14(OR)Y (E14 = Ge, Sn; R = Me2NCH2CH2; Y = Cl, AcO, (Me3Si)2N), and the ate-complexes Li(+)[E14(OCH2CH2NMe2)3](–) and [Li(thf)2](+)[TsiE14(SBu)2](–) (E14 = Ge, Sn; Tsi = (Me3Si)3C), are presented. It was established for the first time that germanium(ii) and tin(ii) derivatives can be stabilized in the monomeric form only through the intramolecular Nsp3E14 coordination bonds and the -acceptor effect of the oxygen atoms without introduction of bulky substituents.  相似文献   

4.
D(CH2CH2S)2MSNH(C6H4) (M = Ge, Sn; D = O, S) spirocycles were synthesized to analyze the influence of the decrease of the radius of the metal and the change of the hardness of donor atom on the strength of the transannular bond and the hypercoordination of group 14 elements. The compounds were characterized by IR, Raman and NMR (1H, 13C and 119Sn) spectroscopy, EI mass spectrometry and elemental analysis. Monocrystal X-ray diffraction analyses were made for the germanium compounds. The germaspirocycles were five-coordinated and had distorted trigonal bipyramid geometry. In contrast with most of the reported analogous germocanes, the transannular bond is stronger when the donor atom is oxygen, rather than sulfur. O(CH2CH2S)2GeSNH(C6H4) exhibits an intramolecular hydrogen bond formation between the amine group and the transannular oxygen. The presence of this hydrogen bond determines whether the sulfur (O?Ge–S) or the nitrogen (S?Ge–N) of the five-member ring is the axial atom. According to the 119Sn chemical shift, both stannospirocycles were five-coordinated and therefore the presence of the transannular interaction in solution could be suggested.  相似文献   

5.
Anion exchange reactions of four structurally related hydroxy salts, Cu2(OH)3NO3, Mg2(OH)3NO3, Ni2(OH)3NO3 and Zn3(OH)4(NO3)2 are compared and trends rationalised in terms of the strength of the covalent bond between the nitrate group and the matrix cation. Powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and elemental analysis are used to characterise the materials. Replacement of the nitrate anions in the zinc and copper salts with benzoate anions is possible although exchange of the zinc salt is accompanied by modification of the layer structure from one where zinc is exclusively six-fold coordinated to a structure where there is both six- and four-fold zinc coordination. Magnesium and nickel hydroxy nitrates, on the other hand, hydrolyse to their respective metal hydroxides.  相似文献   

6.
Synthesis, Crystal Structures and Spectroscopic Investigations of 3d-Transition Metal Complexes with Bicyclo[2.2.1]hept-5-ene-2-endo,3-cis-dicarboxylic Acid and N,N-Donor Ligands The synthesis of coordination compounds of the general type [MLdam(H2O)3] · 2.5 H2O with M = Mn2+, Co2+, Ni2+; H2L = bicyclo[2.2.1]hept-5-ene-2-endo,3-cis-dicarboxylic acid and dam = 2,2′-dipyridyl, 1,10-phenanthroline has been described. The complexes have been characterized by elementary analysis, infrared and electronic spectra and magnetic susceptibility measurements. The results of X-ray crystal structure analyses of [MnLdipy(H2O)3] · 2.5 H2O ( 1 a ) and [CoLdipy(H2O)3] · 2,5 H2O ( 1 b ) show, that both compounds crystallize isotypically and prove the octahedral coordination of the metal atoms. The dicarboxylate anion is coordinated to the central atom by an O atom of only one carboxylate group, the other one is in the ionic state. One O atom of each carboxylate group makes an intramolecular hydrogen bond with a water molecule of the coordination sphere. The other crystal water molecules form a network of H bonds one with another and with the complex molecules, thus stabilizing the crystal packing.  相似文献   

7.
A weakly associated hexamer is formed for [GaCp*] (Cp*=C5Me5) in the solid state (see picture). The recent X-ray crystal structure analyses of [GaCp*] as well as the monomeric InI and TlI compounds [M(2,4,6-Trip3C6H2)] (Trip=2,4,6-iPr3C6H2) throw new light on the association and aggregation of monovalent Group 13 elements in the solid state. The synthesis of [Ni0{In[C(SiMe3)3]}4], a complex with terminally bonded InIR ligands, offers alternative σ-donor/π-acceptor ligands to organometallic chemists. The newest results in this area are likely to open up new and intriguing possibilities in the preparation of main group–transition metal clusters.  相似文献   

8.
Two new dinuclear MnII cluster-based metal-organic frameworks, namely [Mn2(L)(DMPU)3]n ( 1 ) and [Mn(L)0.5(4,4'-bipy)0.5(H2O)]n ( 2 ) (H4L = biphenyl-3,3',5,5'-tetracarboxylic acid, DMPU = 1,3-dimethyltetrahydropyrimidin-2(1H)-one, 4,4'-bipy = 4,4'-bipyridine), were solvothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and magnetic studies. Compound 1 crystallizes in the monoclinic P21/n space group and displays a 3D framework with 4-connected crb/BCT -type topology, and compound 2 crystallizes in the monoclinic C2/c space group and displays a 3D framework with (4,6)-connected sqc422 -type topology. The magnetic studies of compounds 1 and 2 show the presence of weak antiferromagnetic interactions within the dinuclear MnII units.  相似文献   

9.
The reactions of octachlorocyclotetraphosphazatetraene, N4P4Cl8 (1) with difunctional aliphatic reagent, HO-(CH2)5-OH (3) have aroused a good deal of attention, and four types of products have been realized: one 2-open chain-(1′-oxy-5′-hidroxy-pentane)-2,4,4,6,6,8,8-heptachlorocylotetraphosphazatetraene, N4P4Cl7[O(CH2)5OH] (4); one 2,2-mono-spiro-(1′,5′-pentanedioxy)-4,4,6,6,8,8-hexachlorocyclotetraphosphazatetraene, N4P4Cl6[O(CH2)5O] (5); its isomers 2,4-mono-ansa-((1′,5′-pentanedioxy)-2,4,6,6,8,8- hexachlorocyclotetraphosphazatetraene (6) and 2,6-mono-ansa-(1′,5′-pentanedioxy)-2,4,6,6,8,8-hexachlorocyclotetraphosphazatetraene (7); one 2,2,6,6-dispiro-(1′,5′-pentanedioxy)-4,4,8,8-tetrachlorocyclo- tetraphosphazatetraene, N4P4Cl4[O(CH2)5O]2 (8); two isomeric 2,4,6,8-bisansa-(1′,5′-pentanedioxy)-2,4,6,8-tetrachlorocyclotetraphosphazatetraene (9) and 2,6,4,8-bisansa-(1′,5′-pentanedioxy)-2,4,6,8-tetrachloro-cyclotetraphosphazatetraene (10); one 4,4,8,8-dispiro-2,6-ansa- (1′,5′-pentanedioxy)-2,6-dichlorocyclotetra-phosphazatetraene, N4P4Cl2[O(CH2)5O]3 (11), one 2,2,4,4,6,6-trispiro-(1′,5′-pentanedioxy)-8,8-dichlorocyclo-tetraphosphazatetraene, N4P4Cl2[O(CH2)5O]3 (12); and a 2,2,4,4,6,6,8,8-tetraspiro-(1′,5′-pentanedioxy)-cyclotetraphosphazatetraene derivative, N4P4[O(CH2)5O]4, (13). The respective structures were deduced by means of elemental analysis, mass spectrum, and 31P, 1H, and 13C nuclear magnetic resonance spectroscopic investigations.  相似文献   

10.
New intermetallic rare earth compounds LaRhMg, CeRhMg, PrRhMg, and NdRhMg were prepared by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. LaRhMg crystallizes with the LaNiAl type structure, space group Pnma, Z = 8, a = 760.1(2), b = 419.92(8), c = 1702.6(2) pm, wR2 = 0.0482, 740 F2 values and 38 variable parameters. The cerium compound adopts the ZrNiAl structure: P6¯2m, Z = 3, a = 752.3(1), c = 417.6(1) pm, wR2 = 0.0497, 250 F22 values and 17 variable parameters. PrRhMg and NdRhMg crystallize with the TiNiSi type: Pnma, Z = 4, a = 721.62(7), b = 415.98(4), c = 869.47(8) pm, wR2 = 0.1864, 440 F2 values, 20 variables for PrRhMg and a = 720.6(1), b = 417.6(1), c = 868.8(1) pm, wR2 = 0.0779, 425 F2 values, 22 variables for NdRhMg. Refinements of the occupancy parameters revealed mixed Mg/Rh occupancy for the magnesium sites of the cerium and the neodymium compound leading to the compositions CeRh1.262(8)Mg0.738(8) and NdRh1.114(9)Mg0.886(9) for the investigated single crystals. From a geometrical point of view, the four crystal structures are built up from different rhodium centered trigonal prisms. The rhodium and magnesium atoms form three‐dimensional [RhMg] networks in which the rare earth metal atoms are located in different types of channels. The networks show Rh—Mg and Mg—Mg bonding.  相似文献   

11.
New intermetallic rare earth compounds REAuMg (RE = Y, La–Nd, Sm, Eu, Gd–Yb) were synthesized by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. Some structures were refined on the basis of single crystal data. The compounds with Y, La–Nd, Sm, and Gd–Tm adopt the ZrNiAl type structure with space group P62m: a = 770.8(2), c = 419.5(1) pm, wR2 = 0.0269, 261 F2 values for PrAuMg, a = 750.9(2), c = 407.7(1) pm, wR2 = 0.0561, 649 F2 values for HoAuMg with 15 variables for each refinement. Geometrical motifs in HoAuMg are two types of gold centered trigonal prisms: [Au1Mg3Ho6] and [Au2Mg6Ho3]. The gold and magnesium atoms form a three‐dimensional [AuMg] polyanion in which the holmium atoms fill distorted hexagonal channels. The magnesium positions show a small degree of magnesium/gold mixing resulting in the refined compositions PrAu1.012(2)Mg0.988(2) and HoAu1.026(3)Mg0.974(3). EuAuMg and YbAuMg contain divalent europium and ytterbium, respectively. Both compounds crystallize with the TiNiSi type structure, space group Pnma: a = 760.6(3), b = 448.8(2), c = 875.8(2) pm, wR2 = 0.0491, 702 F2 values, 22 variables for EuAuMg, and a = 738.4(1), b = 436.2(1), c = 864.6(2) pm, wR2 = 0.0442, 451 F2 values, and 20 variables for YbAuMg. The europium position shows a small degree of europium/magnesium mixing, and the magnesium site a slight magnesium/gold mixing leading to the refined composition Eu0.962(3)Au1.012(3)Mg1.026(3). No mixed occupancies were found in YbAuMg where all sites are fully occupied. In these structures the europium(ytterbium) and magnesium atoms form zig‐zag chains of egde‐sharing trigonal prisms which are centered by the gold atoms. As is typical for TiNiSi type compounds, also in EuAuMg and YbAuMg a three‐dimensional [AuMg] polyanion occurs in which the europium(ytterbium) atoms are embedded. The degree of distortion of the two polyanions, however, is different.  相似文献   

12.
The synthesis, crystal structure, photophysical properties, and biological activity of the novel bis‐cyclometalated complexes [Ir(ptpy)2(vnsc)] ( 2 ) and [Ir(ptpy)2(acsc)] ( 3 ) [ptpy = 2‐(p‐tolyl)pyridinato, vnsc = vanillin semicarbazone, acsc = acetone semicarbazone] are described. The new compounds were prepared by the reaction of [{Ir(μ‐Cl)(ptpy)2}2] ( 1 ) with the corresponding semicarbazone ligands under basic conditions. The molecular structure of compound 3 was confirmed by a single‐crystal X‐ray diffraction study. The complex crystallized from chloroform as a mono‐ solvate in the orthorhombic space group Pcab with eight molecules in the unit cell.  相似文献   

13.
The chiral compound (H2cydiampy)[RuCl3(p‐cymene)]2 has been obtained in high yield by treating [RuCl2(p‐cymene)]2 with an excess of hydrochloric acid in the presence of one equivalent of N,N′‐bis‐(6‐methylpyrid‐2‐yl)‐(1R,2R)‐1,2‐diaminocyclohexane (cydiampy). It crystallizes in the chiral tetragonal space group P43212, with half of the atoms of the dication related to the other half by a crystallographic C2 axis that also makes equivalent the two anionic metal moieties. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

14.
Synthesis and Crystal Structures of Ln3I(SiS4)2 (Ln = Pr, Nd, Sm, Tb) Single crystals of Ln3I(SiS4)2 were prepared by a two‐step reaction of lanthanide metal, sulfur, silicon and iodine in the ratio 1 : 3.25 : 1 : 0.33 in quartz glass tubes. The thiosilicates crystallize in the monoclinic space group C 2/c (Z = 4) isotypic to Ce3I(SiS4)2 [1]. In the crystal structures the iodide ions form chains along [001] with trigonal coordination by lanthanide ions.  相似文献   

15.
Structures of Bis(trifluoromethyl)halogeno and thiocyanato Mercurates, [Hg(CF3)2X] (X = Br, I, SCN), and a Comparison of the Structural Parameters of the CF3 Groups [(18‐C‐6)K]2[Hg(CF3)2SCN]2 (1) and [P(CH3)(C6H5)3]2[Hg(CF3)2X]2 (X = Br (2) , I (3) ) are prepared and their crystal structures are determined. [(18‐C‐6)K]2[Hg(CF3)2SCN]2 (1) crystallizes in the monoclinic space group P21/c with Z = 2, [P(CH3)(C6H5)3]2[Hg(CF3)2Br]2 (2) in the monoclinic space group P21/n with Z = 2 and [P(CH3)(C6H5)3]2[Hg(CF3)2I]2 (3) in the triclinic space group P1¯ with Z = 1. In the solid state the three compounds form dimeric anions with planar Hg2X2 rings. The structural parameters of the Hg(CF3)2 units in the till now known bis(trifluoromethyl)halogeno mercurates are compared. In all compounds one nearly symmetric and one distorted CF3 group exist. The largest differences of the C—F bond lengths is found for [(18‐C‐6)K][Hg(CF3)2I]. This can be regarded as the experimental evidence for the properties of trifluoromethyl mercury compounds to act as excellent difluorocarbene sources in the presence of alkali iodides.  相似文献   

16.
New intermetallic rare earth iridium silicides Sm3Ir2Si2, HoIrSi, and YbIrSi were synthesized by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. HoIrSi and YbIrSi crystallize in a TiNiSi type structure, space group Pnma: a = 677.1(1), b = 417.37(6), c = 745.1(1) pm, wR2 = 0.0930, 340 F2 values for HoIrSi, and a = 667.2(2), b = 414.16(8), c = 742.8(2) pm, wR2 = 0.0370, 262 F2 values for YbIrSi with 20 parameters for each refinement. The iridium and silicon atoms build a three‐dimensional [IrSi] network in which the holmium(ytterbium) atoms are located in distorted hexagonal channels. Short Ir–Si distances (246–256 pm in YbIrSi) are indicative for strong Ir–Si bonding. Sm3Ir2Si2 crystallizes in a site occupancy variant of the W3CoB3 type: Cmcm, a = 409.69(2), b = 1059.32(7), c = 1327.53(8) pm, wR2 = 0.0995, 383 F2 values and 27 variables. The Ir1, Ir2, and Si atoms occupy the Co, B2, and B1 positions of W3CoB3, leading to eight‐membered Ir4Si4 rings within the puckered two‐dimensional [IrSi] network. The Ir–Si distances range from 245 to 251 pm. The [IrSi] networks are separated by the samarium atoms. Chemical bonding in HoIrSi, YbIrSi, and Sm3Ir2Si2 is briefly discussed.  相似文献   

17.
Fifteen new ternary antimonides T5T' 1‐xSb2+x were synthesized by reaction of the elemental components in an arc‐melting furnace. They crystallize with a tetragonal structure first reported for Nb5SiSn2 (space group I4/mcm, Z = 4.) A structure refinement from four‐circle X‐ray diffractometer data of Hf5Fe1‐xSb2+x (a = 1086.0(1) pm, c = 550.1(1) pm, R = 0.033 for 270 structure factors and 18 variable parameters) showed deviations from the ideal occupancy for two atomic sites, resulting in the composition Hf4.929(3)Fe0.67(1)Sb2.33(1). Structure refinements from X‐ray powder data resulted in the formula Ti5Ni0.45(2)Sb2.55(2), while no deviation from the ideal composition was observed for Ti5RhSb2. The crystal structures of these compounds are discussed together with those of related binary and ternary compounds.  相似文献   

18.
Two tetranuclear compounds [Ln4Na(μ4‐OH)(TC4A)2(acac)4] [Ln = Tb ( 1 ), Eu ( 2 )] (acac = acetylacetonate) were synthesized and characterized based on ptert‐butylthiacalix[4]arene (H4TC4A). Compounds 1 and 2 are isostructural and crystallize in the monoclinic C2/c space group. There are two crystallographically independent metal atoms in one asymmetric unit. Ln1, Ln2, and two metal atoms generated by the symmetry operation are bridged by one μ4‐OH group to form a planar tetragonal Ln44‐OH) unit. Each Ln44‐OH) unit is surrounded by four acac anions and two disordered sodium ions in the planar direction. The upper and lower positions of the Ln44‐OH) unit are further coordinated by two cone‐shaped TC4A ligands to form a sandwich‐type molecular structure. Luminescent measurements reveal that both compounds 1 and 2 exhibit good photoluminescent properties. Moreover, the static and dynamic magnetic properties of compound 1 were also investigated, which demonstrates that 1 is one functional material candidate combining luminescent and antiferromagnetic properties in one molecule.  相似文献   

19.
The MeCOCH2CMe2 ligand in X3SnCMe2CH2COMe ( 2 ; X = halide) acts as a C,O‐chelating group both in the solid state and in non‐coordinating solutions. The intramolecular Sn? O bond lengths in trigonal bipyramidal 2 (X = Cl and I), as determined by X‐ray crystallography, indicate that the stronger interaction occurs in 2 X = Cl. Comparisons with the Sn? O bond lengths in the estertin trihalides, X3SnCH2CH2CO2R ( 1 ; R = Me), suggest that the latter form stronger chelates than do 2 . In chlorocarbon solution, 2 (X = Cl, I) undergoes exchange reactions, as shown by NMR spectra, to give all possible halide derivatives, ∑(ClnI3?nSnCMe2CH2COMe) (n = 0–3). Various ab initio calculations on 2 and X3SnCH2CH2COMe ( 3 ) have been carried out. Comparisons of the theoretical and experimental structures of 2 for X = Cl or I are reported. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

20.
A new compound Ce12Pt7In was synthesized and its crystal structure at 300 K has been determined from single crystal X-ray data. It is tetragonal, space group I4/mcm, Z=4, with the lattice parameters: a=12.102(1) Å and c=14.542(2) Å, wR2=0.1102, 842 F2 values, 33 variable parameters. The structure of Ce12Pt7In is a fully ordered ternary derivative of the Gd3Ga2-type. Isostructural compounds has been found to form with Pr (a=11.976(1) Å, c=14.478(2) Å), Nd (a=11.901(1) Å, c=14.471(2) Å), Gd (a=11.601(3) Å, c=14.472(4) Å), and Ho (a=11.369(1) Å, c=14.462(2) Å). Magnetic properties of Ce12Pt7In, Pr12Pt7In and Nd12Pt7In were studied down to 1.7 K. All three ternaries order magnetically at low temperatures with complex spin arrangements. The electrical resistivity of Ce12Pt7In and Nd12Pt7In is characteristic of rare-earth intermetallics.  相似文献   

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