Bis(2, 2, 2-trichloroethoxy)cobalt(II) and chloro(2, 2, 2-trichloroethoxy) cobalt(II): synthesis and coordination chemistry

Summary Bis(2, 2, 2-trichloroethoxy) cobalt(II) and chloro(2, 2, 2-trichloroethoxy)cobalt(II) [Co(OCH₂CCl₃)₂·L] and [CoCl(OCH₂CCl₃)·L], derivatives (L=tetrahydrofuran, dioxan, triphenylarsine oxide, or pyridine) have been synthesised and characterized. They have tetrahedral geometry both in solution and in the solid state.     

Theoretical study of the structure and stability of dimers (LiBO)2, (LiAlO)2, (LiBS)2, and (LiAlS)2

Institute of New Chemical Problems, Russian Academy of Sciences, Chernogolovka. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 1, pp. 10–17, January–February, 1992.     

Polydentate N(2)S(2)O and N(2)S(2)O(2) Ligands as Alcoholic Derivatives of (N,N'-Bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II) and (N,N'-Bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctane)nickel(II)

The synthesis, structural characterization, spectroscopic, and electrochemical properties of N(2)S(2)-ligated Ni(II) complexes, (N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), and (N,N'-bis(2-mercapto-2-methylpropane)1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), derivatized at S with alcohol-containing alkyl functionalities, are described. Reaction of (bme-daco)Ni(II) with 2-iodoethanol afforded isomers, (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-O,N,N',S,S')halonickel(II) iodide (halo = chloro or iodo), 1, and (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-N,N',S,S')nickel(II) iodide, 2, which differ in the utilization of binding sites in a potentially hexadentate N(2)S(2)O(2) ligand. Blue complex 1 contains nickel in an octahedral environment of N(2)S(2)OX donors; X is best modeled as Cl. It crystallizes in the monoclinic space group P2(1)/n with a = 12.580(6) ?, b = 12.291(6) ?, c = 13.090(7) ?, beta = 97.36(4) degrees, and Z = 4. In contrast, red complex 2 binds only the N(2)S(2) donor set forming a square planar nickel complex, leaving both -CH(2)CH(2)OH arms dangling; the iodide ions serve strictly as counterions. 2 crystallizes in the orthorhombic space group Pca2(1) with a = 15.822(2) ?, b = 13.171(2) ?, c = 10.0390(10) ?, and Z = 4. Reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol affords another octahedral Ni species with a N(2)S(2)OBr donor set, ((5-hydroxy-3,7-dithianonadiyl)-1,5-diazacyclooctane-O,N,N',S,S')bromonickel(II) bromide, 3. Complex 3 crystallizes in the orthorhombic space group Pca2(1) with a = 15.202(5) ?, b = 7.735(2) ?, c = 15.443(4) ?, and Z = 4. Complex 4.2CH(3)CN was synthesized from the reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol. It crystallizes in the monoclinic space group P2/c with a = 20.348(5) ?, b = 6.5120(1) ?, c = 20.548(5) ?, and Z = 4.     

The superconductor (Tl,Hg,Ca)2(Ba,Sr)2(Ca,Sr,Tl)Cu2O7.6

In the title 2212‐type superconductor (thallium mercury calcium barium strontium copper oxide), which contains both Tl and Hg in the charge reservoir (CR), Sr is located at both alkali‐earth (AE) metal sites. Ca enters the CR at the same time as Tl shares the smaller AE site, which increases the apical Cu—Cu distance significantly. The structure causes the superconducting Cu–O layers to become significantly puckered.     

Synthesis,Crystal Structure and Properties of [Mn(hdpa)2(N(CN)2)2] and [Co(hdpa)2(N(CN)2)2] (hdpa = 2, 2'‐Dipyridylamine)

Two new transition metal(II) complexes [M(hdpa)₂(N(CN)₂)₂] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) ų for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)ų for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)^— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated.     

New layered materials: syntheses, structures, and optical properties of K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiaAg(2)S(4), Cs(2)TiAg(2)sS(4), and Cs(2)TiCu(2)Se(4)

The new compounds K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiAg(2)S(4), Cs(2)TiAg(2)S(4), and Cs(2)TiCu(2)Se(4) have been synthesized by the reactions of A(2)Q(3) (A = K, Rb, Cs; Q = S, Se) with Ti, M (M = Cu or Ag), and Q at 823 K. The compounds Rb(2)TiCu(2)S(4), Cs(2)TiAg(2)S(4), and Cs(2)TiCu(2)Se(4) are isostructural. They crystallize with two formula units in space group P4(2)/mcm of the tetragonal system in cells of dimensions a = 5.6046(4) A, c = 13.154(1) A for Rb(2)TiCu(2)S(4), a =6.024(1) A, c = 13.566(4) A for Cs(2)TiAg(2)S(4), and a =5.852(2) A, c =14.234(5) A for Cs(2)TiCu(2)Se(4) at 153 K. Their structure is closely related to that of Cs(2)ZrAg(2)Te(4) and comprises [TiM(2)Q(4)(2)(-)] layers, which are separated by alkali metal atoms. The [TiM(2)Q(4)(2)(-)] layer is anti-fluorite-like with both Ti and M atoms tetrahedrally coordinated to Q atoms. Tetrahedral coordination of Ti(4+) is rare in the solid state. On the basis of unit cell and space group determinations, the compounds K(2)TiCu(2)S(4) and Rb(2)TiAg(2)S(4) are isostructural with the above compounds. The band gaps of K(2)TiCu(2)S(4), Rb(2)TiCu(2)S(4), Rb(2)TiAg(2)S(4), and Cs(2)TiAg(2)S(4) are 2.04, 2.19, 2.33, and 2.44 eV, respectively, as derived from optical measurements. From band-structure calculations, the optical absorption for an A(2)TiM(2)Q(4) compound is assigned to a transition from an M d and Q p valence band (HOMO) to a Ti 3d conduction band.     

Further Examples of the P-O-P Connection in Borophosphates: Synthesis and Characterization of Li(2) Cs(2) B(2) P(4) O(15) , LiK(2) BP(2) O(8) , and Li(3) M(2) BP(4) O(14) (M=K, Rb)

A new series of anhydrous mixed alkali-metal borophosphates-Li(2) Cs(2) B(2) P(4) O(15) (1), LiK(2) BP(2) O(8) (2), Li(3) K(2) BP(4) O(14) (3), and Li(3) Rb(2) BP(4) O(14) (4)-have been successfully synthesized by using the conventional solid-state reaction method. Compound 1 contains a novel fundamental building unit (FBU), [B(4) P(8) O(30) ], with B/P=1:2. Compound 2 contains an FBU of [B(2) P(4) O(16) ] with B/P=1:2. Compounds 3 and 4 are isotypic, and they have a [B(P(2) O(7) )(2) ] unit as their FBU. In all four compounds, their FBUs are connected through corner sharing to generate layered anionic partial structures, and then further linked with metallic polyhedra to form three-dimensional (3D) frameworks. Most interestingly, three of the four compounds contain direct P-O-P connections in their structures, which is extremely rare among borophosphates. Thermal analyses, IR spectroscopy, and UV/Vis/near-IR diffuse reflectance spectroscopy have also been performed on the four title compounds.     

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.     

Structural characterization of CeO(2)-ZrO(2)/TiO(2) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) mixed oxide catalysts by XRD, Raman spectroscopy, HREM, and other techniques

Structural characteristics of CeO(2)-ZrO(2)/TiO(2) (CZ/T) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) (V/CZ/T) mixed oxide catalysts have been investigated using X-ray diffraction (XRD), BET surface area, Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques. The CeO(2)-ZrO(2) (1:1 mole ratio) solid solution was deposited over a finely powdered TiO(2) support by a deposition precipitation method. A nominal 5 wt % V(2)O(5) was impregnated over the calcined (773 K) CZ/T mixed oxide carrier by a wet impregnation technique. The obtained CZ/T and V/CZ/T samples were further subjected to thermal treatments from 773 to 1073 K to understand the dispersion and temperature stability of these materials. In the case of CZ/T samples, the XRD results suggest the formation of different cubic and tetragonal Ce-Zr-oxide phases, Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), Ce(0.5)Zr(0.5)O(2), and Ce(0.16)Zr(0.84)O(2) in varying proportions depending on the treatment temperature. With increasing calcination temperature from 773 to 1073 K, the intensity of the lines pertaining to cubic Ce(0.6)Zr(0.4)O(2) and Ce(0.5)Zr(0.5)O(2) phases increased at the expense of cubic Ce(0.75)Zr(0.25)O(2), indicating more incorporation of zirconia into the ceria lattice. The TiO(2) was mainly in the anatase form whose crystallite size also increased with increasing treatment temperature. A better crystallization and more incorporation of zirconia into the ceria lattice was noted when CZ/T was impregnated with V(2)O(5). However, no crystalline V(2)O(5) could be seen from both XRD and RS measurements. In particular, a preferential formation of CeVO(4) compound and an intense tetragonal Ce(0.16)Zr(0.84)O(2) phase were noted beyond 873 K. The HREM results indicate, in the case of CZ/T samples, a well-dispersed Ce-Zr-oxide of the size approximately 5 nm over the bigger crystals ( approximately 40 nm) of TiO(2) when treated at 873 K. The exact structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic fluorite geometry and the TiO(2) is in anatase form. A better crystallization of Ce-Zr-oxides ( approximately 8 nm) over the surface of bigger crystals of TiO(2) was noted at 1073 K. A further enhancement in the crystallite size and zirconia-rich tetragonal phase was noted in the case of V/CZ/T samples. Further, the structure of CeVO(4) formed was also clearly identified in conformity with XRD and RS results.     

Copper(II) complexes of 2-formyl-, 6-methyl-2-formyl- and 2-benzoylpyridine N(4)-(2-methylpyridinyl)-,N(4)-(2-ethylpyridinyl)-and N(4)-methyl(2-ethylpyridinyl)thiosemicarbazones

Summary The title complexes of general formula [Cu(HL)Cl₂] or [Cu(L)Cl] have been isolated and characterized by ¹H and ¹³C-n.m.r., i.r. and electronic spectra. The i.r., electronic and e.s.r. spectral data for the Cu^II complexes are compared with those of previously studied complexes. The antitumour and antiviral activities of the thiosemicarbazones and their complexes are discussed.     

Structural characterization of nanosized CeO(2)-SiO(2), CeO(2)-TiO(2), and CeO(2)-ZrO(2) catalysts by XRD, Raman, and HREM techniques

Structural characteristics of nanosized ceria-silica, ceria-titania, and ceria-zirconia mixed oxide catalysts have been investigated using X-ray diffraction (XRD), Raman spectroscopy, BET surface area, thermogravimetry, and high-resolution transmission electron microscopy (HREM). The effect of support oxides on the crystal modification of ceria cubic lattice was mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahighly dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO(2)-SiO(2) sample primarily consists of nanocrystalline CeO(2) on the amorphous SiO(2) surface. Both crystalline CeO(2) and TiO(2) anatase phases were noted in the case of CeO(2)-TiO(2) sample. Formation of cubic Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) (at 1073 K) were observed in the case of the CeO(2)-ZrO(2) sample. Raman measurements disclose the fluorite structure of ceria and the presence of oxygen vacancies/Ce(3+). The HREM results reveal well-dispersed CeO(2) nanocrystals over the amorphous SiO(2) matrix in the cases of CeO(2)-SiO(2), isolated CeO(2), and TiO(2) (anatase) nanocrystals, some overlapping regions in the case of CeO(2)-TiO(2), and nanosized CeO(2) and Ce-Zr oxides in the case of CeO(2)-ZrO(2) sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO(2) is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of the mixed oxide systems is more than that of pure CeO(2) and is system dependent.     

Syntheses,structures, and fluxionality of blue luminescent zinc(II) complexes: Zn(2,2',2"-tpa)Cl2, Zn(2,2',2"-tpa)2(O2CCF3)2, and Zn(2,2',3"-tpa)4(O2CCF3)2 (tpa = tripyridylamine)

Three novel Zn(II) complexes containing either 2,2',2"-tripyridylamine (2,2',2"-tpa) or 2,2',3"-tripyridylamine (2,2',3"-tpa) have been synthesized and structurally characterized. Compound 1, Zn(2,2',2"-tpa)Cl2, has a tetrahedral geometry while compounds 2, Zn(2,2',2"-tpa)2(O2CCF3)2, and 3, Zn(2,2',3"-tpa)4(O2CCF3)2, have an octahedral geometry. The 2,2',2"-tpa ligand in 1 and 2 functions as a bidentate ligand, chelating to the zinc center, while the 2,2",3"-tpa ligand in 3 functions as a terminal ligand, binding to the zinc center through the 3-pyridyl nitrogen atom. All three compounds emit a blue color in solution and in the solid state. The emission maxima for the three compounds in solution are at lambda = 422, 426, and 432 nm, respectively. The blue luminescence of the complexes is due to a pi *-->pi transition of the tpa ligand as established by an ab initio calculation on the free ligand 2,2',2"-tpa and complex 1. Compounds 1 and 2 are fluxional in solution owing to an exchange process between the coordinate and noncoordinate 2-pyridyl rings of the 2,2',2"-tpa ligand. Compound 2 is also fluxional owing to a cis-trans isomerization process, as determined by variable-temperature 1H NMR spectroscopic analysis.     

Mercurous Dimethylglyoximato Nitrate,Hg2(Dmg)2(NO3)2

Colourless needles of mercurous dimethylglyoximato nitrate, Hg₂(Dmg)₂(NO₃)₂, grow from a diluted nitric acid solution of mercurous nitrate and dimethylglyoxime. The crystal structure (triclinic, P1¯, a = 728.50(13), b = 1066.8(2), c = 1167.9(2) pm, α = 93.78(2)°, β = 94.16(2)°, γ = 98.61(2)°, R_all = 0, 0726) contains the cations [Hg₂(Dmg)₂]²⁺ and “non‐coordinating” (NO₃)^— anions. In the cation, two neutral dimethylglyoxime molecules coordinate bidentately with Hg—N distances in the narrow range of 236 to 239 pm to the mercurous ion, Hg₂²⁺, which exhibits a Hg—Hg bond distance of 252.23(8) pm).     

Synthesis and catalytic epoxidation activity with TBHP and H2O2 of dioxo-, oxoperoxo-, and oxodiperoxo molybdenum(VI) and tungsten(VI) compounds containing monodentate or bidentate phosphine oxide ligands: crystal structures of WCl2(O)2(OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2.C4H10O, WCl2(O)2dppmO2, Mo(O)(O2)2dppmO2, and W(O)(O2)2dppmO2

The dioxo tungsten(VI) and molybdenum(VI) complexes WCl2(O)2(OPMePh2)2, WCl2(O)2dppmO2, and MoCl2(O)2dppmO2, the oxoperoxo compounds WCl2(O)(O2)(OPMePh2)2, WCl2(O)(O2)dppmO2, and MoCl2(O)(O2)dppmO2, and the oxodiperoxo complexes, W(O)(O2)2dppmO2 and Mo(O)(O2)2dppmO2 have been prepared and characterized by IR spectroscopy, 31P NMR spectroscopy, elemental analysis, and X-ray crystallography. The structural and X-ray crystallographic data of compounds WCl2(O)2(OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2.4H10O, WCl2(O)2dppmO2, Mo(O)(O2)2dppmO2, and W(O)(O2)2dppmO2 are also detailed. All complexes were studied as catalysts for cis-cyclooctene epoxidation in the presence of tert-butyl hydroperoxide (TBHP) or H2O2 as an oxidant. The Mo-based catalysts showed a superior reactivity over W-based catalysts in the TBHP system. On the other hand, in the H2O2 system, the W-based catalysts (accomplishing nearly 100% epoxidation of cyclooctene in 6 h) are more reactive than the Mo catalysts (<45% under some conditions). Various solvent systems have been investigated, and ethanol is the most suitable solvent for the H2O2 system.     

配合物构型、配体结构及反式效应对Ru(Ⅱ)吡啶类配合物中NO2配体在酸催化下反应机理的影响

顺-Ru(bpy)2(NO2)2和反-Ru(bpy)2(NO2)2(bpy=2,2-联吡啶)组成完全相同,但配合物的构型不同.反-Ru(bpy)2(NO2)2和反-Ru(py)4(NO2)2(PY=吡啶)两个配合物构型相同,辅助配体相同,但主配体有差异.本文通过在不同或相似条件下,上述三个配合物中辅助配体NO2-在酸催化下的反应结果的对比,探讨了配合物中的NO2-在酸催化下的反应机理(缔合或解离)与配合物构型、配体结构以及配体反式效应性质之间的关系.当反应配体对位为NO2-等反式效应较强的基团时,反应倾向于以解离机理发生配体取代反应.若对位为OH-等反式效应较弱的基团时,倾向于发生No2-配体的分解反应.在顺式联吡啶二硝基化合物中.酸催化下只发生配体分解反应.通过对比得出,处于反应配体(No2-)反位的配体的性质,特别是反式效应性质的强弱,会明显影响或改变配体取代反应的机理(解离或缔合)或反应类型(取代或分解),有时甚至是影响反应机理或反应方式的主要因素.无论在反式还是在顺式构型的配合物中,bpy的约束构型会影响过渡态的稳定性,进而影响反应发生的机理.     

Diamino-di-tert-butylsilane als Bausteine cyclischer (SiN)2−, (SiNBN)2−, (SiN2Sn)- und spirocyclischer (SiN2)2Si-, (SiN2Sn)2S-Verbindungen

Diamino-di-tert-butylsilanes - Building Blocks for Cyclic (SiN)₂, (SiNBN)₂, (SiN₂Sn), and Spirocyclic (SiN₂)₂Si, (SiN₂Sn)₂S Compounds The aminochlorosilanes (Me₃C)₂SiClNHR ( 1 : R?H, 2 : R?Me) are obtained by the ammonolysis ( 1 ) respectively aminolysis ( 2 ) of di-tert-butyldichlorosilane in the n-hexane. The dilithium derivative of diamino-di-tert-butylsilane reacts with FSiMe₂R′ ( 3 : R′?Me, 4 : R′?F) in a molar ratio 1 : 2 to give the 1,3,5-trisilazanes 3 and 4 , (Me₃C)₂SiNHSiMe₂R′, in a molar ratio 1 : 1 with F₃SiN(SiMe₃)₂ to give the 1,3-diaza-2,4-disilacyclobutane 5 , (Me₃C)₂Si(NH)₂SiFN(SiMe₃)₂, and with F₂BN(SiMe₃)₂ to give the 1,3,5,7-tetraaza-2,6-dibora-4,8-disilacyclooctane 6 , [(Me₃C)₂SiNH-BN(SiMe₃)₂-NH]₂. The dilithium derivative of di-tert-butyl-bis(methylamino)silane reacts with SiF₄ with formation of the 1,3,5-trisilazane 7 , (Me₃C)₂Si(NMeSiF₃)₂, and the spirocycic compound 8 , [(Me₃C)₂Si(NMe)₂]₂Si, with SnCl₂ the cyclosilazane 9 , (Me₃C)₂SiNMe₂ is obtained. The dilithium derivative of 3 reacts with SnCl₂ to give the cyclo-1,3-diaza-2-sila-4-stannylen 10 , (Me₃C)₂Si(NSiMe₃)₂Sn. The oxidation of 10 with elemental sulfur leads to the formation of the spirocyclus 11 , [(Me₃C)₂Si(NSiMe₃)₂SnS]₂.     

Syntheses,Spectroscopic Studies,and Crystal Structures of Me2Sn(O2PPh2)2, Ph2Pb(O2PMe2)2, and Ph2Pb(O2PPh2)2

Me₂Sn(O₂PPh₂)₂ ( 1 ), Ph₂Pb(O₂PMe₂)₂ ( 2 ), and Ph₂Pb(O₂PPh₂)₂ ( 3 ) have been synthesized by the reactions of Me₂SnCl₂ or Ph₃PbCl with the corresponding diorganophosphinic acid in methanol. X‐ray diffraction studies show that the diorganophosphinate groups behave as double bridges between the metal atoms leading to polymeric ring‐chain structures with M₂O₄P₂ (M = Pb, Sn) eight‐membered rings. The organic groups bonded to the metal atoms are in trans‐position in the resulting octahedral arrangement around the metal atoms. The IR and the mass spectra were reported and discussed.