Synthesis and Characterization of （CH3CH2CH2CH2NH3）2SnBr6

1 INTRODUCTION Recently, the researches on inorganic-organic hy-brid compounds represent an advanced field in mate-rial science[1]. At the molecular level, the combina-tion of two extremely different components providesan avenue to design new hybrid materials as well asthe ability to modulate properties of one or more ofthe components[2～6]. Some attractive properties, suchas efficient luminescence[2～4], ideal thermal and me-chanical stability, interesting magnetic[5], non-linearoptical[…     

Über die Darstellung der Dimercapto(methyl)sulfonium-Salze[CH3S(SH)2]+AsF−6 und [CH3S(SH)2]+SbCl−6 und der Bis(chlorthio)Methylsulfonium-Salze [CH3S(SCI)2]+ AsF6−und [CH3S(SCL)2]+SbCl−6

On the Preparation of Dimercapto(methyl)Sulfonium Salts [CH₃S(SH)₂]⁺ AsF₆^? and [CH₃S(SH)₂]⁺SbCl₆^? and the Bis(chlorothio)methylsulfonium Salts [CH₃S(SCI)₂]⁺ AsF₆^? and [CH₃S(SCI)₂]⁺ SbCl₆^? The preparation of the dimercapto(methyl)sulfonium salts [CH₃S(SH)₂]⁺ AsF₆^? and [CH₃S(SH)₂]⁺SbCl₆^? from [CH₃SCl₂]⁺ salts and H₂S at 195 K is reported. The salts are stable below 210 K. They are characterized by additional Raman spektroscopic measurements of the isotopic labelled cations [CH₃S(SD)₂]⁺, [CH₃S(³⁴SH)₂]⁺ and [CH₃S(₃₄SD)₂]⁺. The dimercapto(methyl)sulfonium salts are transfered into bis(chlorthio)methylsulfonium salts by reaction with Cl₂ at 195 K.     

A Novel Alkene(alkyl)(aqua)(aryl)platinum(II) Complex – [Pt{CH(CH2C6F5)CH2CH2CH=CH2}(C6F5)(OH2)]

From the reaction of PtCl₂(hex) (hex = hexa‐1,5‐diene) with LiC₆F₅ in diethyl ether, the complex [Pt{CH(CH₂C₆F₅)CH₂CH₂CH=CH₂}(C₆F₅)(OH₂)] ( 1 ) was isolated. The crystal structure (monoclinic, C2/c (no. 15), Z = 8, a = 15.241(3), b = 16.579(2), c = 16.225(2) Å, β = 111.12(2)°) shows a complex with square planar coordination around platinum with a template formed 1‐pentafluorophenylhex‐5‐en‐2‐yl ligand, and C₆F₅ and aqua ligands trans to the double bond and alkyl carbon, respectively.     

Interpretation der Schwingungsspektren von (CH3)2SO2, (CH3)2SO(NH) und (CH3)2S(NH)2 unter Verwendung eines Kopplungsstufenverfahrens

Normal Coordinate Analysis of (CH₃)₂SO₂, (CH₃)₂SO(NH), and (CH₃)₂S(NH)₂ using the Method of Stepwise Coupling The qualitative assignment of the vibrational spectra of (CH₃)₂SO₂ ( 1 ), (CH₃)₂SO(NH) ( 2 a ), and (CH₃)₂S(NH)₂ ( 3 a ) and of the C and N deuterated derivatives of 2 a and 3 a is used in a normal coordinate analysis by the method of stepwise coupling. The force constants and the energy distributions are calculated in symmetry coordinates using a generalized valence force field.     

Self-assembly of the octanuclear cluster [Cu8(OH)10(NH2(CH2)2CH3)12]6+ and the one-dimensional N-propylcarbamate-linked coordination polymer {[Cu(O2CNH(CH2)2CH3)(NH2(CH2)2CH3)3](ClO4)}n

The reaction of Cu(ClO4)2.6-H2O and n-propylamine in methanol gives two high-nuclearity products of well-defined compositions. At amine concentrations greater than seven equivalents compared to copper ion concentration, the system fixes carbon dioxide from air to form the one-dimensional carbamate-bridged coordination polymer, {[Cu(mu2-O,O'-O2CNH(CH2)2CH3)(NH2(CH2)2CH3)3](ClO4)}n ({1-ClO4}n). Lower relative amine concentrations lead to the self-assembly of an octanuclear copper-amine-hydroxide cluster [Cu8(OH)10(NH2(CH2)2CH3)12]6+ (2). Both compounds exhibit unique structures: {1-ClO4}n is the first mu2-O,O'-mono-N-alkylcarbamate-linked coordination polymer and 2 is the largest copper-hydroxide-monodentate amine cluster identified to date. The crystal structures indicate that the size of the n-propyl group is probably crucial for directing the formation of these compounds. Magnetic susceptibility studies indicate very weak antiferromagnetic coupling for 1. The octanuclear cluster 2 displays slightly stronger net antiferromagnetic coupling, despite the presence of a number of Cu-O(H)-Cu angles below the value of about 97 degrees that would normally be expected to yield ferromagnetic coupling.     

Molecular and crystal structures of Ph2P(O)(CH2)2OH and Ph2P(O)CH2(C6H6)OH

The molecular and crystal structures of Ph₂P(O)(CH₂)₂OH and Ph₂P(O)CH₂(C₆H₆)OH have been determined. For the first compound the space group is with unit cell dimensions a=10.505(2), b=13.720(2), c=14.782(3) Å; =72.58(6), =76.95(6), =72.49(6)° for Z=6 (Syntex diffractometer,MoK radiation, 2996 reflections, R=3.2%). The second compound crystallizes in the space group P2₁2₁2₁ with unit cell dimensions a=9.371(3), b=9.014(3), c=18.461(5) Å for Z=4 (DAR-UM diffractometer,CuK radiation, 909 reflections, R=4.9%). In Ph₂P(O)(CH₂)₂OH, three independent molecules differing in structural details are linked by the P=O...O hydrogen bonds (O...H is 1.84, 1.80, and 1.86 Å), to form a chain. In Ph₂P(O)CH₂(C₆H₆)OH, the molecules are joined by pairs of the P=O...H–O bonds (O...H is 1.81 Å) to form 16-membered dimeric associates.Institute of Chemical Physics, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 109–118, May–June 1993.Translated by T. Yudanova     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Die Kristallstrukturen der silylierten Phosphanimine Me3SiNP(c-C6H11)3 und (Me3SiNPPh2)2CH2

Crystal Structures of the Silylated Phosphaneimines Me₃SiNP(c-C₆H₁₁)₃ and (Me₃SiNPPh₂)₂CH₂ The crystal structures of Me₃SiNP(c-C₆H₁₁)₃ ( 1 ) and (Me₃SiNPPh₂)₂CH₂ ( 2 ) are determined by X-ray diffraction at single crystals. In both compounds the PN distances correspond to double bonds, the SiN distances to single bonds. With 149.8° the SiNP bond angle in 1 is noticeably large, while it is only 138.5° in 2 , which shows C₂ symmetry. 1 : Space group P2₁/n, Z = 4, lattice dimensions at –70 °C: a = 1143.0(1), b = 1743.0(2), c = 1152.5(1) pm, β = 90.42(1)°; R = 0.0677. 2 : Space group I4₁/a, Z = 8, lattice dimensions at –60 °C: a = b = 1959.7(1), c = 1695.8(1) pm, R = 0.0433.     

New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes

The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.     

New polyfunctional silicon-containing amines C6[CH2CH2SiMe(OCH2CH2NR2)2]6 (R = H,Me) and their reactions with cobalt(ii) chloride and dicobalt octacarbonyl

Hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene and hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene C₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆ (4, R = H; 5, R = Me) were prepared from hexakis(methyldichlorosilylethyl)benzene C₆(Cl₂MeSiCH₂CH₂)₆ and 2-aminoethanol or N,N-dimethyl-2-aminoethanol, respectively. Compounds 4 and 5 react with anhydrous cobalt (ii) chloride to give poorly soluble dodecachloro{hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene}hexacobalt and dodecachloro{hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene}hexacobalt {Co₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}Cl₁₂ (R = H or Me), respectively. Polyfunctional amine 4 reacts with dicobalt octacarbonyl to produce hexakis[bis(2-aminoethoxy)methylsilylethyl]benzenedicobalt(ii) tetrakis(tetracarbonylcobaltate) {Co₂[(NH₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}[Co(CO)₄]₄. N,N-Dimethyl-substituted polyfunctional amine 5 is lowly reactive in the reaction with Co₂(CO)₈, whereas the simplest model of this compound, viz., bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane (NMe₂CH₂CH₂O)₂SiMe₂, slowly reacts with Co₂(CO)₈ to give tris[bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane]cobalt(ii) bis(tetracarbonylcobaltate) {Co[(NMe₂CH₂CH₂O)₂SiMe₂]₃}[Co(CO)₄]₂. Thermal decomposition and transformations of the resulting complexes under the action of oxygen and water were studied.     

Vibrational study of (CH3)4NSbCl6 and [(CH3)4N]2SiF6

(CH3)4NSbCl6 and [(CH3)4N]2SiF6 are face-centred cubic compounds at ambient temperature with a = 11.548 and 11.172 A, respectively. The vibrational spectra of these two compounds are discussed in relation to their crystal structure and other compounds containing (CH3)4N+ ions. The assignment of the observed bands is discussed. The Raman and infrared spectra of [(CH3)4N]2SiF6 show that the cations and anions are not distorted inside the crystals and are weakly hydrogen-bonded to each other. The infrared spectrum of (CH3)4NSbCl6 confirms a cubic structure for this compound at ambient temperature, in which cations are in octahedral environments and can be interpreted as being disordered groups. No evidence could be found for the existence of hydrogen bonding between cations and anions in this compound. The phase transition of (CH3)4NSbCI6 is studied by means of Raman spectroscopy. It is believed to be governed by the reorientational motions of tetramethylammonium cations and may be classified as an 'order-disorder' type.     

Neubestimmung der Kristallstrukturen der Hexahydroxometallate Na2Sn(OH)6, K2Sn(OH)6 und K2Pb(OH)6

Redetermination of the Crystal Structures of the Hexahydroxometallates Na₂Sn(OH)₆, K₂Sn(OH)₆, and K₂Pb(OH)₆ Slow cooling down of hot saturated hydroxo stannate‐ resp. ‐plumbate solutions gives crystals of Na₂Sn(OH)₆, K₂Sn(OH)₆, and K₂Pb(OH)₆ well suited for an X‐ray structure determination. With these crystals the so far known crystal data were verified, determined more precisely and H‐positions found for the first time. The compounds crystallize rhombohedral in the space group R 3. The hexagonal unit cells contain three formula units with Na₂Sn(OH)₆: a = 5.951(1) Å, c = 14.191(2) Å, c/a = 2.384 K₂Sn(OH)₆: a = 6.541(1) Å, c = 12.813(4) Å, c/a = 1.959 K₂Pb(OH)₆: a = 6.625(1) Å, c = 12.998(2) Å, c/a = 1.962 The compounds are not isotypic whereas the atoms occupy in all three cases the same Wyckoff positions. Na₂Sn(OH)₆ has with an hcp packing of O a CdI₂ like superstructure with Na and Sn in octahedral interstices. Hydrogen bonds O–H…O–H play a role in solid K₂Sn(OH)₆ and K₂Pb(OH)₆. In these compounds the potassium ions are shifted from an octahedral coordination in an hcp packing of O. They have nine nearest O‐neighbours. The hydrogen bonds are investigated by Raman spectroscopy.     

Thermal decomposition of di-t-butyl peroxide in the presence of (CH3)2CCH2: Reactions of CH3, (CH3)2ĊCH2CH3, and (CH3)2ĊCH2C(CH3)2CH2CH3 radicals

A study of the reaction initiated by the thermal decomposition of di-t-butyl peroxide (DTBP) in the presence of (CH₃)₂C?CH₂ (B) at 391–444 K has yielded kinetic data on a number of reactions involving CH₃ (M·), (CH₃)₂CCH₂CH₃ (MB·) and (CH₃)₂?CH₂C(CH₃)₂CH₂CH₃ (MBB·) radicals. The cross-combination ratio for M· and MB· radicals, rate constants for the addition to B of M· and MB· radicals relative to those for their recombination reactions, and rate constants for the decomposition of DTBP, have been determined. The values are, respectively, where θ = RT ln 10 and the units are dm^3/2 mol^?1/2 s^?1/2 for k₂/k and k₉/k, s^?1 for k₀, and kJ mol^?1 for E. Various disproportionation-combination ratios involving M·, MB·, and MBB· radicals have been evaluated. The values obtained are: Δ₁(M·, MB·) = 0.79 ± 0.35, Δ₁(MB·, MB·) = 3.0 ± 1.0, Δ₁(MBB·, MB·) = 0.7 ± 0.4, Δ₁(M·, MBB·) = 4.1 ± 1.0, Δ₁(MB·, MBB·) = 6.2 ± 1.4, and Δ₁(MBB·, MBB·) = 3.9 ± 2.3, where Δ₁ refers to H-abstraction from the CH₃ group adjacent to the center of the second radical, yielding a 1-olefin. © 1994 John Wiley & Sons, Inc.     

CH3NH2(CH2)2NH2CH3][M2(HCOO)6] (M = MnII and CoII): weak ferromagnetic metal formate frameworks of unique binodal 6-connected (4(12).6(3))(4(9).6(6)) topology, templated by a diammonium cation

Two compounds of [dmenH(2)(2+)][M(2)(HCOO)(6)(2-)] (M = Mn(II) and Co(II)), synthesized using N,N'-dimethylethylenediammonium (dmenH(2)(2+)) as the template, possess anionic metal formate frameworks of a novel binodal 6-connected (4(12).6(3))(4(9).6(6)) topology. They are the first coordination examples of this unique network closely related to niccolite and colquiriite and exhibit 3D long-range antiferromagnetic ordering with small spin canting.     

Polymer imprinting with iron-oxo-hydroxo clusters: [Fe6O2(OH)2(O2CC(Cl)=CH2)12(H2O)2], [Fe6O2(OH)2(O2C-Ph-(CH)=CH2)12(H2O)2] and [{Fe(O2CC(Cl)=CH2)(OMe)2}10

We report the syntheses of imprinted polymers using iron-oxo-hydroxo clusters as templates. Three new iron clusters, [Fe(6)O(2)(OH)(2)(O(2)CC(Cl)=CH(2))(12)(H(2)O)(2)] (1), [{Fe(O(2)CC(Cl)=CH(2))(OMe)(2)}(10)] (2) and [Fe(6)O(2)(OH)(2)(O(2)C-Ph-(CH)=CH(2))(12)(H(2)O)(2)] (3) have been prepared from commercially-available carboxylic acids. Cluster-imprinted-polymers (CIPs) of 1, 2 and 3 were prepared with ethylene glycol dimethacrylate monomer, and of 1 with methyl methacrylate monomer. The imprinted sites within the CIPs were examined using EXAFS and diffuse reflectance UV/vis spectroscopy, demonstrating that the clusters 1, 2 and 3 were incorporated intact within the polymers. Extraction of the clusters from the CIPs imprinted with 1 and 3 gave new polymers that showed evidence of an imprinting effect.