Synthesis and Crystal Structure of Bis[(2,6-pyridinedicarboxylato)(methanol)dibenzyltin(IV)]

ＩｎｔｒｏｄｕｃｔｉｏｎＤｉｏｒｇａｎｏｔｉｎｄｅｒｉｖａｔｉｖｅｓｏｆ 2 ,6 ｐｙｒｉｄｉｎｅｄｉｃａｒｂｏｘｙｌｉｃａｃｉｄｅｘｈｉｂｉｔｈｉｇｈｉｎｖｉｔｒｏａｎｔｉｔｕｍｏｕｒａｃｔｉｖｉｔｉｅｓ .1 5Ｔｈｅｓｅｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄｂｙｔｈｅｒｅａｃｔｉｏｎｏｆｄｉｏｒｇａｎｏｔｉｎｄｉｃｈｌｏｒｉｄｅｓｏｒｄｉｏｒｇａｎｏｔｉｎｏｘｉｄｅｓｗｉｔｈ 2 ,6 ｐｙｒｉｄｉｎｅｄｉｃａｒｂｏｘｙｌｉｃａｃｉｄ ,ｂｕｔｔｈｅｒｅａｃｔｉｏｎｂｅｔｗｅｅｎｔｒｉ …     

Polyfluorothiolate derivatives of rhodium(I). Crystal and molecular structure of [Rh(μ-SC6HF4)(C8H12)]2

Summary The thiolato-bridged dinuclear compounds [Rh(-SR)-(COD)]₂, where R=p-C₆HF₄ (1),p-C₆H₄F (2) and CF₃ (3), are obtained from the chloro-bridged analogue by ligand exchange.Compound (1) crystallizes in the space group P₁ with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, =103.87(3)°, =106.98(3)° and =105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(-SR)(CO)₂]₂ (4), (5) and (6) are obtained, but addition of PPh₃ affords the monomeric species [Rh(SR)(PPh₃)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh₃ vary with the nature of R; [Rh(-SR)(PPh₃)(CO)]₂ is obtained when R=p-C₆H₄F (10) and CF₃ (11) but monomeric [Rh(SR)-(PPh₃)(CO)₂] (12) is produced when R=p-C₆HF₄. The latter mononuclear compounds, with R=p-C₆H₄F (13) and CF₃ (14), are also formed by reaction of [Rh(SR)-(PPh₃)(COD)] with CO.     

Crystal structure of [Pd3(μ-OH)(μ-CH3COO)5]

The crystals of the [Pd₃(μ-OH)(μ-CH₃COO)₅] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) ų, space group Pna2₁, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd₃(μ-OH)(μ-CH₃COO)₅], in which the OH^? group, together with five CH₃COO^? anions, is a bridge ligand.     

Synthesis and structure of μ-oxo-bis-[(2,5-dimethylbenzenesulfonato)tri-p-tolylantimony(v)]

μ-Oxobis[(2,5-dimethylbenzenesulfonato)tri-p-tolylantimony(v)] was prepared by the reaction of 2,5-dimethylbenzesulfonic acid with tri-p-tolylstibine in the presence of hydrogen peroxide. According to X-ray diffraction data, the linear O bridge links two Sb atoms having a trigonal bipyramidal configuration. The 2,5-dimethylbenzenesufonate group and the bridging O atom occupy the axial positions and the three tolyl substituents are equatorial. The Sb(1)−O−Sb(2) and O−Sb−O angles are 180.0(0)° and 177.2(1)°; the Sb−C(Ph)_eq, Sb−O(SO₂Ar), and Sb−μ−O distances are 2.090(5)–2.095(6), 2.258(3), and 1.9361(5), respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2346–2349, December, 1999.     

Synthesis and characterisation of phosphinothiolate tin(IV) complexes. Crystal structure of [SntBu2(OPPh2C6H4S)(OH2)]ClO4·H2O

[SnR₂Cl₂] (R=Me, ^tBu) react with OPPh₂C₆H₄SH in the presence of NaOEt affording mononuclear derivatives [SnR₂(OPPh₂C₆H₄S)₂] (1,  2) with two units of the oxide of the thiophenylphosphine. The loss of one of such units is achieved by the reaction of 1 and 2 with HCF₃SO₃ or HClO₄ giving rise to complexes with the formula [SnR₂(OPPh₂C₆H₄S)]A (A=CF₃SO₃, ClO₄) (3a–b, 4a–b). The crystal structure of [Sn^tBu₂(OPPh₂C₆H₄S)]ClO₄ (4b) has been determined by X-ray diffraction.     

Mono- and dinuclear palladium(II) compounds containing nitrogen ligands. Crystal and molecular structure of [Pd(N,C-dmba)(NCO)(2,3-lut)] and [Pd(H2CCOMe)Cl(2,2′-bipy)]

The cyanate-bridged cyclopalladated compound [Pd(N,C-dmba)(-NCO)]₂ (1)(dmba = PhCH₂NMe₂) reacts in CH₂Cl₂ with 2,3-lutidine (2,3-lut), 3,4-lutidine (3,4-lut), 2,2-bipyridine (2,2-bipy) and 4,4-bipyridine (4,4-bipy), to give [Pd(N,C-dmba)(NCO)(2,3-lut)](2), [Pd(N,C-dmba)(NCO)(3,4-lut)](3), [{Pd(N,C-dmba)(NCO)}₂(-2,2-bipy)]· CH₂Cl₂ (4) and [{Pd(N,C-dmba)(NCO)}₂(-4,4-bipy)]· CH₂Cl₂ (5), respectively. The compounds were characterized by elemental analysis, i.r. and n.m.r. spectroscopy and also by t.g.a. The i.r. spectra of (2–5) display typical bands of monodentate N-bonded cyanate groups, whereas the n.m.r. data of (4) are consistent with the presence of a bridging 2,2-bipyridine ligand. Complex (4) decomposes slowly in acetone. One of the products formed, [Pd(H₂CCOMe)Cl(2,2-bipy)](6), was characterized by X-ray diffraction. As inferred from the t.g.a., the thermal stability decreases in the order:[{Pd(N,C-dmba)(NCO)}₂(-4,4-bipy)].CH₂Cl₂ (5) > [Pd(N,C-dmba)(2,3-lut)(NCO)](2)=[Pd(N,C-dmba)(3,4-lut)(NCO)](3) > [{Pd(N,C-dmba)(NCO)}₂(-2,2-bipy)]· CH₂Cl₂ (4). According to thermal analysis and X-ray diffraction patterns compounds (2–3) decompose into metallic palladium Pd(0), whereas (4–5) decompose with the formation of PdO. The X-ray crystal and molecular structure of [Pd(N,C-dmba)(NCO)(2,3-lut)](2) was determined. The lutidine unit is perpendicular to the coordination plane.     

Synthesis of single and double butterfly iron carbonyl complexes by reactions of [(μ-RSe)(μ-CO)Fe2(CO)6]− anions. Crystal structures of (μ-p-MeC6H4Se)[μ-PhCH2N(H)CS]Fe2(CO)6 and [(μ-PhSe)(μ-MeAs)Fe2(CO)6]2

The in situ reactions of the [Et₃NH]⁺ and [MgBr]⁺ salts of [(μ-RSe)(μ-CO)Fe₂(CO)₆]⁻ (1) anions with PhC(Cl)NPh gave single butterfly complexes (μ-RSe)(μ-PhCNPh)Fe₂(CO)₆ (2, R=Ph; 3, R=p-MeC₆H₄; 4, R=Et), whereas those of the [Et₃NH]⁺ salts of 1 with R′NCS afforded single butterfly complexes (μ-RSe)[μ-R′N(H)CS]Fe₂(CO)₆ (5, R=Ph, R′=Ph; 6, R=p-MeC₆H₄ R′=Ph; 7, R=p-MeC₆H₄, R′=PhCO; 8, R=p-MeC₆H₄, R′=PhCH₂). Compound 8 could also be prepared by reaction of the [MgBr]⁺ salt of 1 (R=p-MeC₆H₄) with PhCH₂NCS followed by treatment with CF₃CO₂H. More interestingly, while the [Et₃NH]⁺ salt of 1 (R=Ph) reacted with Et₃OBF₄ to give a carbyne ligand-bridged single butterfly complex (μ-PhSe)(μ-EtOC)Fe₂(CO)₆ (9), reaction of the [Et₃NH]⁺ salt of 1 (R=Ph) with MeAsI₂ produced a MeAsAsMe ligand-bridged double butterfly complex [(μ-PhSe)(μ-MeAs)Fe₂(CO)₆]₂ (10). All the new complexes, 2–10, were characterized by elemental analysis and various spectroscopic methods, for complexes 8 and 10, the structures were also confirmed by X-ray diffraction techniques.     

Syntheses and molecular structures of organo-tellurium(IV) halides trans-[(Ph2Te)(μ-Cl)2]n,cis-[(Ph2Te)(μ-Cl)2]n, [(p-MeC6H4)2TeBr2], and [{(p-MeC6H4)2TeBr}2(μ-O)]

Abstract

Treatment of Ph₂Te with aqueous hydrogen chloride under air in refluxing THF gave trans-[(Ph₂Te)(μ-Cl)₂]_n (1), whereas interaction of Ph₂Te with ammonium chloride under similar condition afforded cis-[(Ph₂Te)(μ-Cl)₂]_n (2). Reaction of (p-MeC₆H₄)₂Te and bromine in refluxing THF resulted in formation of a discrete complex [(p-MeC₆H₄)₂TeBr₂] (3) with a step-like tetrameric structure, which further reacted with sodium hydroxide in refluxing THF to give a dinuclear tellurium oxide [{(p-Me-C₆H₄)₂TeBr}₂(μ-O)] (4) with a bridging oxygen atom. Complexes 1–4 have been spectroscopically characterized and their crystal structures have been established by X-ray crystallography.     

Synthesis and catalytic activity of DI-μ-methoxo-bis[(2-aminopyridine)(chloro)copper(II)] and m-xylylenediamine Zn(OAc)2

Compound I, [di-μ-methoxo-bis[(2-aminopyridine)(chloro)copper(II)], was obtained by two different synthetic routes. In synthetic route 1, we first obtained intermediate by the addition of two equivalents of o-aminopyridine to copper chloride in an ethanolic solution, and then we recrystallized the intermediate from methanol and n-hexane to give compound I. Synthetic route 2 involved the reaction of o-aminopyridine with copper chloride in a methanol solution directly. The crystal structure of compound I was obtained. The reaction of m-xylylenediamine with Zn(OAc)₂ · 2H₂O in THF resulted in the production of one novel zinc complex C₁₂H₁₈N₂O₄Zn, bis(m-xylenediamine)zinc (II) and its structure was determined by X-ray diffraction analysis. Complexes I and II were also characterized by elemental analysis, and IR. Then they were applied as catalysts for the Henry reaction, and they achieved good conversions (64 and > 99%, respectively).     

Synthesis and Crystal Structure of {(PPh3)2ClRu(μ-Cl)-Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O)

The title compound has been synthesized by the reaction of [RuCl2(PPh3)3] and closo-[B10H10]2- in (CH3)2CHOH solution. Crystals suitable for a single crystal X-ray diffraction analysis were obtained from n-pentane diffused to CH2Cl2 solution. The crystal {(PPh3)2ClRu(μ-Cl)Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O) is monoclinic , space group P21/n , Mr=1359.47, with a=19.434(4), b =14.340(4), c=25.865(9)(A), β= 95.48(3)°, V=7175(4)(A)3, Dc=1.258 g/cm3, Z=4, λ(MoKα)=0.71073(A),μ=6.03 cm-1, F(000)=2784, R=0.0631, wR2= 0.1425, S=1.001. The title compound is a bimetallic species in which the second ruthenium center is bound to the cluster {(PPh3)RuB10H7[OCH(CH3)2]3} via an Ru-Cl-Ru and two Ru-H-B-Ru bridges. The third isoproxy group replaces a hydrogen atom on B(10) of the cage, which indicates the activity of the cage.     

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)]

The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)( μ3-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a=15.563(3), b=8.9547(18), c=17.846(4) (A), β=101.29(3)°, V=2438.9(9) (A)3, Z=4, Dc=1.878 g/cm3, T=193(2) K, C20H30ClCuMo2S4, Mr=689.60, F(000)=1376, μ(MoKα)=2.335 mm–1, S=1.050, R=0.0305 and wR=0.0688 for 4033 observed reflections with Ⅰ ＞ 2σ(Ⅰ). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by oneμ3-S atom, twoμ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) (A), respectively.     

Synthesis and characterization of diorganotin(IV) derivatives from rhodanine (HRd): crystal structures of [(PhCH2)2Sn(Rd)(μ-OH)]2 and [n-Bu2Sn(Rd)(μ-OH)]2

The diorganotin(IV) complexes, [R₂Sn(Rd)(μ-OH)]₂ (R?=?Me (1), PhCH₂ (2), n-Bu (3), Ph (4); HRd?=?rhodanine), have been synthesized and characterized by IR and multinuclear (¹H, ¹³C, ¹¹⁹Sn) NMR spectroscopy. The structures of complexes 2 and 3 have been determined by single-crystal X-ray diffraction. Both crystal structures of 2 and 3 show the presence of asymmetrically bridging hydroxy groups leading to an Sn₂O₂ unit. Each atom in complex 1 is also coordinated by an N atom of ligand and two C atoms of the alkyl groups, so the Sn environment is based on a trigonal bipyramid. While in complex 2, a weak intermolecular Sn–O interaction has also been found between the two adjacent molecules, so the geometry of the Sn atom can be best described as six-coordinate octahedral. The salient feature of the supramolecular structure of complex 3 is that of a 1D polymer, in which the discrete molecules are connected through weak intermolecular Sn?···?O interactions.     

Stereochemical aspects of the conversion of cyclopentadienylruthenium alkoxycarbene to the corresponding acetylide complexes. Crystal structure of [(η-C5H5)Ru(Ph2PCHMeCHMePPh2)(CCPh)]

Reactions of [(η-C₅H₅)Ru(Diphosphine){C(OCH₃)CH₂C₆H₅}]PF₆ complexes with CH₃MgBr give the corresponding phenylacetylide [(η-C₅-H₅)-Ru(Diphosphine)CCC₆H₅] complexes. A crystal structure determination has been carried out for the product in which the diphosphine is rac-1,2-dimethyl-1,2-ethanediylbis(diphenylphosphine). For the complexes in which the diphosphine is (R)-1,2-propanediylbis(diphenylphosphine), the stereo-chemical outcome of the reaction implies retention of configuration at the metal atom.     

Synthesis and characterization of heteronuclear germanium(IV) and lanthanum(III) (chromium(III)) complexes with 1,3-diamino-2-propanoltetraacetic acid: Crystal and molecular structure of [Ge(OH)(μ-Hpdta)(μ-OH)La(H2O)4] · H2O

Two heteronuclear germanium(IV) and lanthanum(III) (chromium(III)) complexes with 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) have been synthesized. The compounds have been characterized by elemental analysis and X-ray powder diffraction data. The structure of [Ge(OH)(??-Hpdta)(??-OH)La(H₂O)₄] · H₂O (I) has been determined by X-ray crystallography. The crystals are monoclinic, a = 9.3805(3) ?, b = 10.3023(4) ?, c = 21.6527(6) ?, ?? = 94.829(2)°, V = 2085.10(12) ?³, Z = 4, space group P2₁/n, R1 = 0.0294 based on 5480 reflections with I > 2??(I). Compound I is composed of binuclear [Ge(OH)(??-Hpdta)(??-OH)La(H₂O)₄] molecules and crystal water molecules. In the dimeric molecule, the germanium and lanthanum atoms are linked by the bridging oxygen atom of the hydroxo ligand and the oxygen atom of the deprotonated isopropanol group of Hpdta^5?. The coordination spheres of germanium and lanthanum each contains one nitrogen atom and two carboxyl oxygen atoms of the four acetate arms of the heptadentate Hpdta^5? ligand. The Ge coordination polyhedron is completed to a distorted octahedron by the oxygen atom of the terminal hydroxo group, and the lanthanum coordination polyhedron is completed to a nine-vertex polyhedron by the oxygen atoms of four water molecules. In crystal, the complex molecules and crystal water molecules are combined by a system of hydrogen bonds.     

Synthesis of Co–Pd alloys by co-electroreduction of aquachloro-cobalt(II) and palladium(II) complexes

The work presents results of the studies on the synthesis of Co–Pd alloys from acid electrolytes containing chloride ions. The main aim of the tests was to identify reactions responsible for alloy formation and to determine an influence of the electrolysis parameters, i.e. working electrode potential, electrolyte composition and temperature on the composition of the resulted alloy coatings. Electrochemical investigations were performed by applying cyclic voltammetry (CV) combined with electrochemical quartz crystal microbalance (EQCM). The electrolyte composition was selected based on a thermodynamic analysis and spectrophotometric tests which were described in our previous papers [1, 2]. They allowed determination of equilibrium distribution of the metals complex forms and a stability analysis of the electrolyte. The alloys were synthesized within the potential range from ?0.7 to ?1.1 V. The tests indicate a possibility of alloys synthesis already at the potential range 相似文献   

Synthesis and Crystal Structure of a Coordination Polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n

The coordination polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n (phth = phthalate, phen = 1,10-phenanthroline) with formula C22H20CoN2O6 (Mr = 467.33) was synthesized by the solvothermal method under low temperature, and its crystal structure was determined by singlecrystal X-ray diffraction. The complex belongs to monoclinic system, space group P21/n with a =12.7352(16), b = 8.8125(11), c = 18.677(2) (A), β = 102.633(2)°, V = 2045.3(4) (A)3, Z = 4, Dc =1.518 g/cm3,μ = 0.882 mm-1, F(000) = 964, S = 1.053, the final R = 0.0401 and wR = 0.0984 for 3135 observed reflections (I ＞ 2σ(I)). Single-crystal X-ray analysis revealed that the Co(Ⅱ) ion is six-coordinated. The cobalt complex forms a one-dimensional chain structure via phthalate bridging ligand. In the cobalt complex, a 3D network structure is formed by π-π stacking interaction of 1,10-phenanthroline as well as intermolecular hydrogen bonding interactions.     

Synthesis and Crystal Structure of Bis(μ-bis(diphenyl-phosphino)methane)(μ-benzenethiolate)(acetonitrile)Dicopper(I) Perchlorate Diethylether Solvate

The reaction between [Cu2(μ-dppm)2(MeCN)4](ClO4)2(dppm=bis(diphenylphos-phino)methane) and [Zn(PhS)2(bpy)] (bpy=2,2'-bipyridine,PhS=benzenethiolate) gave the complex [Cu2(μ-dppm)2(μ-PhS)(MeCN)]ClO4·0.5(Et2O)(C58H52ClNO4P4SCu2·0.5Et2O) which was determined by X-ray single-crystal diffraction.The crystal is of orthorhombic,space group P212121 with a=13.6157(3),b=20.8022(6),c=21.3299(6)A,V=6041.4(3) A3,Mr=1182.54,Dc=1.300 g/cm3,F(000)=2444,μ=0.934 mm-1 and Z=4.The final R=0.0773 and wR=0.1843 for 7744 observed reflections (I>2σ(I)).The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate.One copper atom is in a distorted trigonal bipyramidal environ- ment,whereas the other adopts a distorted tetrahedral geometry.     

Synthesis and magnetic properties of trinuclear nickel(II) complexes bridged by α-benzyldioximato groups

Four new NiII–NiII–NiII homotrinuclear complexes namely [Ni(-BD)2{NiL2}](ClO4)2 [L = 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (5-NO2-phen), 2,2-bipyridyl (bpy) or 4,4-dimethyl-2,2bipyridyl (Me2bpy) and (-BD)– = -benzyldioximato ion] have been prepared and characterized. Based on elemental analyses, i.r. spectra, conductivity measurements, extended -benzyldioximato-bridged systems consisting of three nickel(II) ions in which the central nickel(II) ion has a square-planar environment and the end capped two nickel(II) ions have a distorted octahedral environment are proposed for these structures. The temperature dependence of the magnetic susceptibility for complexes (1) (phen), (2) (5-NO2-phen), (3) (bpy) and (4) (Me2bpy) were measured over the 77–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator (H^ = –2JS^1S^2), giving the exchange integral J = –13.31 cm–1 for (1), J = –7.37 cm–1 for (2), J = –8.96 cm–1 for (3) and J = –7.33 cm–1 for (4) These results indicate a weak antiferromagnetic spin exchange interaction between the two terminal nickel(II) io     

Synthesis and crystal structure of Ba2[(UO2)(C2O4)2(NCS)]NCS·7H2O

Single crystals of Ba₂[(UO₂)(C₂O₄)₂(NCS)]NCS · 7H₂O were prepared and studied by X-ray diffraction. The crystals are monoclinic, space group P2₁/c, Z = 4, a = 13.508(5) Å, b = 12.268(4) Å, c = 14.965(5) Å, β = 115.38(1)°, V = 2240.6(13) ų. The main structural units in the crystal are the island complex species [(UO₂)(C₂O₄)₂(NCS)]^3? corresponding to the crystal chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ^2? , M¹ = NCS^?) of uranyl complexes, which are united into a three-dimensional framework through electrostatic interactions and through hydrogen bonds involving oxalate and isocyanate ions and water molecules.     

Synthesis and Crystal Structure of [Cd(NBA)(μ_3-OH)(4,4′-bipy)_(1/2)]_n

A new cadmium polymer [Cd(NBA)(μ3-OH)(4,4′-bipy)1/2]n 1 (NBA = m-nitrobenzoic acid and 4,4′-bipy = 4,4-bipyridine) has been synthesized by hydrothermal reaction. Its structure was determined by single-crystal X-ray diffraction method, and characterized by elemental analysis and IR spectrum. The crystal is of monoclinic, space group C2/c, with a = 15.6912(9), b = 25.9394(15), c = 6.7332(4) ′, β = 114.7700(10)°, V = 2488.4(3) 3, C12H9CdN2O5, Mr = 373.61, Z = 8, Dc = 1.995 g/cm3, μ = 1.776 mm-1, F(000) = 1464, R = 0.0411 and wR = 0.1128 for 2130 observed reflections (I > 2σ(I)). X-ray diffraction studies reveal that the compound features a layered structure, in which 4,4′-bipy ligands bridge Z type of double chains [Cd(μ3-OH)]n and NBA ligands locate at the two sides of the layer. The π-π interactions between the benzene rings of NBA ligands of two adjacent layers lead to the 3D framework.