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1.
用过氧化物法合成了 [Co(3,3-tri)(amp)Cl][ZnCl4]的两个经式异构体,晶体结构解析表明两者互为差向异构体。其中反式异构体 (仲氢相对于 Cl)晶体属单斜晶系,空间群 C2/c, a=2.7663(7)nm, b=0.9505(1)nm, c=1.8288(4)nm,β =105.57(2)°, V=4.632(1)nm3, Dc=1.706g· cm-3, Z=8, F000=2432.00,μ (MoKα )=23.51cm-1, R=0.033, Rw=0.041;顺式异构体 (仲氢相对于 Cl)晶体属三斜晶系,空间群, a=1.0790(2)nm, b=1.1749(1)nm, c=0.8920(1)nm,α =90.73(1)°,β =109.573(9)°,γ =80.60(1)°, V=1.0500(2)nm3, Dc=1.71g· cm-3, Z=2, F000=548.00,μ (MoKα )=25.73cm-1, R=0.022, Rw=0.030。两异构体中 Co3+为六配位,其差异仅表现在 3,3-tri仲胺上氢的取向不同。 相似文献
2.
Dr. Martin Börner Dr. Jennifer Klose Matias E. Gutierrez Suburu Prof. Cristian A. Strassert Fangshun Yang Dr. Kirill Yu. Monakhov Prof. Dr. Bernd Abel Prof. Dr. Berthold Kersting 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(60):14899-14910
The synthesis, structure, magnetic, and photophysical properties of two dinuclear, luminescent, mixed-ligand [CrIII2L(O2CR)]3+ complexes (R=CH3 ( 1 ), Ph ( 2 )) of a 24-membered binucleating hexa-aza-dithiophenolate macrocycle (L)2− are presented. X-ray crystallographic analysis reveals an edge-sharing bioctahedral N3Cr(μ-SR)2(μ1,3-O2CR)CrN3 core structure with μ1,3-bridging carboxylate groups. A ferromagnetic superexchange interaction between the electron spins of the Cr3+ ions leads to a high-spin (S=3) ground state. The coupling constants (J=+24.2(1) cm−1 ( 1 ), +34.8(4) cm−1 ( 2 ), H=−2JS1S2) are significantly larger than in related bis-μ-alkoxido-μ-carboxylato structures. DFT calculations performed on both complexes reproduce both the sign and strength of the exchange interactions found experimentally. Frozen methanol-dichloromethane 1 : 1 solutions of 1 and 2 luminesce at 750 nm when excited into the 4LMCT state on the 4A2 → 2T1 (ν2) bands (λexc=405 nm). The absolute quantum yields (ΦL) for 1 and 2 were found to be strongly temperature dependent. At 77 K in frozen MeOH/CH2Cl2 glasses, ΦL=0.44±0.02 (for 1 ), ΦL=0.45±0.02 (for 2 ). 相似文献
3.
Herbert Schumann Jrn Winterfeld Esther C. E. Rosenthal Holger Hemling Lothar Esser 《无机化学与普通化学杂志》1995,621(1):122-130
Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(III) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2,6)(SiMe3)}2(THF)], and [ClNd{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] A series of lanthanide(III) amides [Ln{N(C6H5) · (SiMe3)}3(THF)x] [Ln = Y ( 1 ), La ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Tb ( 6 ), Er ( 8 ), Yb ( 9 ), Lu ( 10 )] could be prepared by the reaction of lanthanide trichlorides, LnCl3, with LiN(C6H5)(SiMe3). Treatment of NdCl3(THF)2 and LuCl3(THF)3 with the lithium salts of the bulky amides [N(C6H3R2-2,6)(SiMe3)]? (R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2, 6)(SiMe3)}2(THF)] ( 11 ) and [ClLn{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] [Ln = Nd ( 12 ), Lu ( 13 )], respectively. The 1H- and 13C-NMR and mass spectra of the new compounds as well as the X-ray crystal structures of the neodymium derivatives 3 , 11 and 12 are discussed. 相似文献
4.
The reactions of Al(III), Ga(III) and In(III) nitrates with 2-quinaldic acid (qaH) afforded [Al2(OH)2(qa)4]·2H2O (1), [Ga(qa)2(H2O)2]NO3 (2) and [In(qa)2(NO3)(H2O)] (3), respectively, in high yields. The crystal structures of 1, 2 and 3 have been determined by single-crystal X-ray crystallography. The structure of 1 features a di-hydroxo bridged [Al2(μ-OH)2]4+ dimer in which each Al(III) is further ligated by two bidentate chelate qa? ligands. Complexes 2 and 3 are mononuclear with the M(III) ions in octahedral environments surrounded by two bidentate chelate qa? and two H2O in 2 or one H2O and a terminal NO3? in 3. Characteristic IR as well as thermal analysis and solid-state fluorescence are discussed. 相似文献
5.
以N,N′-二(4-甲氧基水杨基)邻苯二胺(H2L)为配体合成了2个新的稀土配合物[M_2L_3(H_2O)](M=Tb (1),Dy (2)),并对它们进行了红外分析、元素分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为三明治型双核配合物。此外还研究了配合物1和2的磁学性质,结果表明配合物1和2都表现出反铁磁性作用和场诱导效应引起的慢弛豫行为。配合物2的有效能垒和驰豫时间分别为35.45 cm-1和2.7×10~(-10) s。 相似文献
6.
Two 3D Ln-organic coordination frameworks(Ln = Pr3+ for 1 and Er3+ for 2) have been constructed. Single-crystal X-ray diffraction analysis reveals that the two complexes have similar structures and belong to the monoclinic C2/c space group. The trans-μ4-(η2:η1)-(η1:η1) 1,2-pda2- anions link the LnIII centers to generate a 2D network containing helical motif. The dimensionality is extended into a 3D architecture through cis-bis(μ2-η2:η1) 1,2-pda2- anions linking. The geometry of Ln3+ ions is single-capped anti-square prism. Two complexes were characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 2 was also investigated at room temperature. 相似文献
7.
标题化合物 C10H8ClN2O2S2Sb 由[C5H5NH][SbCl4]与 2-巯基氧化吡啶钠盐(Nampo)反应制得。其结构通过元素分析、IR 进行了表征,用 X-射线衍射法测定了该化合物的晶体结构。结果表明,晶体属于三斜晶系, 空间群为 P1, Mr = 409.50, 晶体参数:a = 9.4022(6), b =10.2910(7), c = 14.4631(9) ?, α= 104.321(1), β = 96.978(1), γ = 90.179(1)?, V = 1345.09(15)?3, Z = 4, Dc = 2.022 g/cm3, μ = 2.553 mm–1, F(000) = 792。晶体结构用直接法解出, 经全矩阵最小二乘法修正,最终结构偏离因子 R = 0.0368, wR = 0.0854。化合物分子中, 锑与一个氯原子和两个配体 mpo 配位,形成五配位变形的四角锥构型配合物。在晶胞堆积图中,锑原子又与另一分子中的氯原子以次级键形式作用,形成缺位配位多面体构型。 相似文献
8.
Yasunori Yamada Daishin Koori Kengo Mori Yuuki Oshikawa 《Journal of Coordination Chemistry》2016,69(24):3735-3744
The reaction of N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-pyridylmethyl)-R-1,2-propanediamine (R-bbppnH2) with LnCl3?6H2O (Ln: Lu, Yb) stereoselectively gave an optically active complex, [LnCl(R-bbppn)], which crystallizes in the acentric space group of P212121. The central lutetium(III) is coordinated by two oxygens from two phenolates, four nitrogens from two pyridines, and one bidentate propanediamine of R-bbppn2?, one chloride to form a seven-coordinate distorted pentagonal bipyramidal geometry. Although two optical isomers, ΔΛΔ and ΛΔΛ, are possible for such a structure, the absolute configuration of the complex is stereoselectively unified to ΔΛΔ. The coordinated chloride of the complex is readily replaced by other ligands, and hence the reaction with thiocyanate results in formation of another seven-coordinate complex, [Ln(NCS)(R-bbppn)]. 相似文献
9.
Trans,trans-[MoX2py4][MoX4py2] (X = Cl, A; Br, B; py = pyridine, C5H5N) are the side products of reaction of between (NH4)2[MoX5 · H2O] (X = Cl,Br) with pyridine diluted with methanol. Both trans,trans-[MoX2py4][MoX4py2] are monoclinic, P21/n space group, with z = 2 and: a = 12.568(1), b = 9.430(1), c = 14.952(1) Å and β = 100.81(1)° (A); a = 12.551(2), b = 9.533(2), c = 15.366(2) (Å) and β = 99.35(1) (B). Cations and anions are located on the symmetry centers and have eclipsed conformation of the trans located pyridine ligands. Average Mo? X and Mo? N (pyridine) bonds are; (cation) 2.41, 2.21 Å (A); 2.54, 2.21 Å (B); (anion) 2.44, 2.20 Å (A); 2.58, 2.20 Å (B). Anionic part of the compounds can be oxidised by bromine to trans-MoX4py2, which precipitates from the solution. Cation can be isolated from the solution in the form of trans-[MoX2py4]Br3 (X = Cl, Br). The compounds were also characterised by chemical analysis, infrared spectroscopy and conductivity measurements. 相似文献
10.
Treatment of (2-C5H4N)CH2 3N (TPA) with one equivalent of MCl2 in n-BuOH at elevated temperatures affords the six-coordinate complexes [(TPA)MCl2] (M = Co (1), Fe (2)) and, in the case of CoCl2, the five-coordinate chloride salt [(TPA)CoCl]Cl (3). Conversely, addition of an excess of CoCl2 in the latter reaction leads to [(TPA)CoCl]2[CoCl4] (4) as the only isolable product. Interaction of one equivalent of (2-C5H4N)CH2 2NH (DPA) and MCl2 under similar reaction conditions to that described above affords the dimeric species [(fac-DPA)MCl(μ-Cl)]2 (M = Co (5), Fe (6)), while the bis(ligand) halide salts [(fac-DPA)2M]Cl2 (M = Co (7), Fe (8)) are accessible on addition of two equivalents of DPA. In the presence of air, 6 undergoes oxidation to give [ (fac-DPA)FeCl2 2(μ-O)] (9). Single-crystal X-ray diffraction studies are reported for 1, 2 · MeCN, 3, , 7 · 3MeCN, 8 · 3MeCN and 9. 相似文献
11.
In this study, the sandwich complex of tmtaa, Y(tmtaa) (Htmtaa)·2THF (H2tmtaa=6,8,15,17-tetramethyldibenzo [b,i]
, respectively. The distances of the yttrium to the planes of the 4 nitrogen atoms for tmtaa and Htmtaa are 1.44 (2) and 1.51 (2) Å, respectively. 相似文献
12.
Christina D. Polyzou Helen Nikolaou Catherine P. Raptopoulou Konstantis F. Konidaris Vlasoula Bekiari Vassilis Psycharis Spyros P. Perlepes 《Molecules (Basel, Switzerland)》2021,26(6)
The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln2(O2CMe)4(NO3)2(mepaoH)2] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the LnIII—mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O2CMe)3·4H2O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy2(O2CMe)6(mepaoH)2] (6). Treatment of 6 with one equivalent of HNO3 gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2–4 display similar structural characteristics with 1 and 5. The structures of 1–5 consist of dinuclear molecules in which the two LnIII centers are bridged by two bidentate bridging (η1:η1:μ2) and two chelating-bridging (η1:η2:μ2) acetate groups. The LnIII atoms are each chelated by a N,N’-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate LnIII centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the TbIII atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0–300 K range reveal weak antiferromagnetic intramolecular GdIII…GdIII exchange interactions in 3; the J value is −0.09(1) cm−1 based on the spin Hamiltonian Ĥ = −J(ŜGd1·ŜGd2). 相似文献
13.
Structures involving unshared electron pair. The Crystal Structures of As(OCOCH3)3 and As2O(OCOCH3)4
As2O(OCOCH3)4, reported now for the first time, was obtained, besides As(OCOCH3)3 by dissolving As2O3 in acetic anhydride. The crystals of As(OCOCH3)3 (A) (monoclinic, space group Cc, Z = 4, a = 9.970(2), b = 13.203(2), c = 8.272(1) Å, β = 117.01(2)°) and of As2O(OCOCH3)4 (B) (monoclinic, space group P21/n, Z = 4, a = 13.966(5), b = 8.127(4), c = 12.706(4) Å, β = 95.14(1)°) are built up from discrete molecules defined by chemical formulae As(OCOCH3)3 and (CH3OCO)2As? O? As(OCOCH3)2, respectively. The molecular structure of both compounds is based on the AsO3 pyramid: in (A) with the As? O bonds of 1.841(6) Å and the O? As? O angle of 89.9(3)° as a mean, in (B) with slightly different values and with the As? O? As angle of 127.7(4)° at the bridging oxygen atom. The additional weak chelating contacts are at the distances As…O from 2.625(9) to 2.745(10) Å in (A) and from 2.72(1) to 2.84(2) in (B). The actual arsenic coordination can be described as very distorted octahedral in (A) and square-pyramidal in (B). 相似文献
14.
Mihaela Badea Rodica Olar Gina Vasile Ana Emandi Veronica Pop Dana Marinescu 《Journal of Thermal Analysis and Calorimetry》2005,81(2):273-276
Summary This paper reports the investigation of the thermal stability of three new complexes of Cr(III) with acrylate anion, [Cr2(C3H3O2)4(OH)2(H2O)4], [Cr3O(C3H3O2)6(C3H4O2)3](C3H3O2)×5H2O and [Cr2(C3H3O2)5(OH)] ×2H2O, respectively. This type of complexes is important in proper carbohydrate and lipid metabolism of mammals. The thermal decomposition steps were evidenced. The thermal transformations are complex processes according to TG and DTG curves including dehydration and oxidative degradation of acrylate ion processes. The final product of decomposition is the chromium(III) oxide. 相似文献
15.
16.
The octahedral cobalt(III) complexes, [Co(L)(int)2]Cl · 3H2O (1), [Co(L)(NCS)2]NCS · H2O (2) and [Co(L)(NCO)2]NCO · H2O (3) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane, int = isonicotinate) were obtained by the reactions of [Co(L)Cl2]Cl · 4H2O with the corresponding ligands. The X-ray analysis of 1 shows that the complex has an octahedral geometry formed by coordination of four secondary amines of the macrocycle and two oxygen atoms of the axial isonicotinate ligands. Complex 2 also has an octahedral geometry with four secondary amines of the macrocycle and two nitrogen atoms of the axial thiocyanate ligands. Electronic spectra of the complexes also exhibit a low-spin octahedral geometry. Cyclic voltammetry of the complexes undergoes a one-electron wave corresponding to a CoIII/CoII process. The electronic spectra and electrochemical behaviors of the complexes are significantly affected by the nature of the axial ligands. 相似文献
17.
Ligand Exchange Reactions of Bis(acetylacetonato)dioxo-molybdenum(VI). Crystal Structures of [Salicylaldehyde-benzoylhydrazonato(2–)]dioxo-methanol-molybdenum(VI) and [Benzoylacetone-benzoylhydrazonato(2–)]dioxo-triphenylphosphaneoxide-molybdenum(VI) The products of ligand exchange reactions between bis(acetylacetonato)dioxo-molybdenum(VI) and tridentate diacidic ligands H2L in the presence of triphenylphosphane were found by mass spectrometry to be complexes of the type MoO2L. In the case of salicylaldehyde 2-hydroxyanil MoL2 could also be identified. The compounds MoO2L were crystallized as complexes with methanol or triphenylphosphane oxide. Crystallographic data see “Inhaltsübersicht”. 相似文献
18.
19.
Victor Wee Lin Ng 《Journal of organometallic chemistry》2005,690(9):2323-2332
The reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with 1 mol equivalent of 2,5-dimercapto-1,3,4-thiadiazole (DMcTH2) at ambient temperature led to the isolation of a reddish-brown crystalline solid of CpCr(CO)3(η1-DMcTH) (5) and a green solid of CpCr(CO)3H (2) in yields of ca. 28% and 30%, respectively, along with some [CpCr(CO)2]2 (3) and [CpCr(CO)2]2S (4). The reaction of 1 with 1 mol equivalent of vinylene trithiocarbonate (SCS(CH)2S) (VTTC) at 90 °C led to the isolation of a red crystalline solid of CpCr(CO)2(η2-SCHSC2H2) (6) in ca. 15% yield while the reaction of 1 with isopropylxanthic disulfide ((CH3)2CHOCS2)2 resulted in the formation of CpCr(CO)2(η2-S2COCH(CH3)2) (8) in ca. 80% yield. The complexes 5, 6 and 8 have been determined by single crystal X-ray diffraction analysis. 相似文献
20.
4‐Methylpyridinium cations, mpyH+, crystallized with complex aqua/chloro/lanthanoid(III) species for the gamut of the rare earth series, have ‘domains of existence’ defined for the following forms:
- (a) The triclinic series (mpyH)2[{(H2O)3Cl3Ln(μ‐Cl)(2|2)}2], previously defined for the Ln = La–Nd members (those for La, Pr characterized by full structure determinations);
- (b) The triclinic series (mpyH)2[(H2O)3LnCl4]Cl, previously defined for the Ln = Eu, Ho members by full structure determinations, is here augmented by the Ln = Nd, Sm examples (full structure determinations, the latter a new ‘light’ Ln extremum);
- (c) A new monoclinic C2/c series (mpyH)2[(H2O)4LnCl3]Cl2, defined for the Ln = Er–Yb extrema (full structural characterizations for the Ln = Er, Tm, Yb members); the lanthanoid‐containing entity (which, with the cations, exhibits some disorder) is a neutral molecule of a new type. For the Ln = Lu case, a fully ordered derivative monoclinic C2 form has been obtained in a cell one half the size.
- (i) For Ln = La, (mpyH)8[{(H2O)3Cl3La(μ‐Cl)(2|2)}2]‐[{(H2O)4Cl2La(μ‐Cl)2La(OH2)2Cl2(μ‐Cl)(2|2)}2]Cl4·6H2O·mpy has been defined by a full structural determination; the binuclear anion is similar to that in (a), albeit with some disorder, with the tetranuclear anion derivative of it.
- (ii) For Ln = Lu, (mpyH)2[(H2O)5LuCl2]Cl3 is defined by a full structure determination.
- (iii) For Ln = Y, (mpyH)2[(H2O)7YCl]Cl4 is defined by a full structure determination; here, and in (ii), the complex component is cationic.