Thermal decomposition of cyano complexes of the type M(NH3)3Ni(CN)4 (M=Cu,Zn, Cd)

Three complex compounds with the compositions Cu(NH₃)₃Ni(CN)₄ (CuA), Zn(NH₃)₃Ni(CN)₄ (ZnA), and Cd(NH₃)₃Ni(CN)₄ (CdA) were prepared and identified. Their structures were examined by the methods of infrared spectroscopy and X-ray powder diffraction and compared with one another. The thermal stabilities and stoichiometries of thermal decomposition were investigated with a derivatograph. It follows from the results that the thermal stability increases in the sequence CuA < ZnA < CdA.

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Zusammenfassung Drei Komplexverbindungen der Zusammensetzung Cu(NH₃)₃Ni(CN)₄ (CuA), Zn(NH₃)₃Ni(CN)₄ (ZnA) und Cd(NH₃)₃Ni(CN)₄ (CdA) wurden dargestellt und identifiziert. Die Strukturen der Verbindungen wurde infrarotspektroskopisch und röntgendiffraktometrisch untersucht und miteinander verglichen. Die thermische Stabilität und die Stöchiometrie der thermischen Zersetzung wurden mittels eines Derivatographen untersucht. Die thermische Stabilität nimmt in der Reihenfolge CuA < ZnA < CdA zu.

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Cu(NH₃)₃Ni(CN)₄ (CuA), Zn(NH₃)₃Ni(CN)₄ (ZnA) Cd(NH₃)₃Ni(CN)₄ (CdA). , . . , CuA     

Metal(II) hexafluorophosphates(V) (M = Sr, Pb) containing XeF(2)-coordinated metal ions [M(XeF(2))(3)](PF(6))(2), [Pb(3)(XeF(2))(11)](PF(6))(6), and [Sr(3)(XeF(2))(10)](PF(6))(6)

From the system MF(2)/PF(5)/XeF(2)/anhydrous hydrogen fluoride (aHF), four compounds [Sr(XeF(2))(3)](PF(6))(2), [Pb(XeF(2))(3)](PF(6))(2), [Sr(3)(XeF(2))(10)](PF(6))(6), and [Pb(3)(XeF(2))(11)](PF(6))(6) were isolated and characterized by Raman spectroscopy and X-ray single-crystal diffraction. The [M(XeF(2))(3)](PF(6))(2) (M = Sr, Pb) compounds are isostructural with the previously reported [Sr(XeF(2))(3)](AsF(6))(2). The structure of [Sr(3)(XeF(2))(10)](PF(6))(6) (space group C2/c; a = 11.778(6) Angstrom, b = 12.497(6) Angstrom, c = 34.60(2) Angstrom, beta = 95.574(4) degrees, V = 5069(4) Angstrom(3), Z = 4) contains two crystallographically independent metal centers with a coordination number of 10 and rather unusual coordination spheres in the shape of tetracapped trigonal prisms. The bridging XeF(2) molecules and one bridging PF(6)- anion, which connect the metal centers, form complicated 3D structures. The structure of [Pb(3)(XeF(2))(11)](PF(6))(6) (space group C2/m; a = 13.01(3) Angstrom, b = 11.437(4) Angstrom, c = 18.487(7) Angstrom, beta = 104.374(9) degrees, V = 2665(6) Angstrom(3), Z = 2) consists of a 3D network of the general formula {[Pb(3)(XeF(2))(10)](PF(6))(6)}n and a noncoordinated XeF(2) molecule fixed in the crystal structure only by weak electrostatic interactions. This structure also contains two crystallographically independent Pb atoms. One of them possesses a unique homoleptic environment built up by eight F atoms from eight XeF(2) molecules in the shape of a cube, whereas the second Pb atom with a coordination number of 9 adopts the shape of a tricapped trigonal prism common for lead compounds. [Pb(3)(XeF(2))(11)](PF(6))(6) and [Sr(3)(XeF(2))(10)](PF(6))(6) are formed when an excess of XeF(2) is used during the process of the crystallization of [M(XeF(2))(3)](PF(6))(2) from their aHF solutions.     

Flexible ligands and structural diversity: isomerism in Cd(NO3)2 coordination polymers

The ligands 1,4-bis(2-pyridylmethylsulfanylmethyl)benzene (L1) and 2,5-bis(2-pyridylmethylsulfanylmethyl)pyrazine (L2) were treated with Cd(NO3)2.4H2O in metal-to-ligand ratios of 1:1 and 2:1, respectively; L2 was also treated with CdCl2.2.5H2O in a 2:1 ratio. All products were found to be coordination polymers. The crystal structures of {[Cd(L1)(NO3)2].CH2Cl2}infinity (1a), {[Cd(L1)(NO3)2].4/3CH3CN}infinity (1b), {[Cd2(L2)(NO3)4].2CH3CN}infinity (2.2CH3CN), and {[Cd2(L2)Cl4].2CH2Cl2}infinity (3.2CH2Cl2) were determined. Compounds 1a and 1b were found to be conformational supramolecular isomers. The structure of 1b displayed topological isomerism with two isomeric polymer chains, 1b(1) and 1b(2), in the one crystal forming a single supramolecular array. The structure of 2.2CH(3)CN showed Cd2(L2) units linked together by nitrates bridging between the Cd(II) centers in a mode previously not seen in Cd(II) compounds. The overall structure of 3.2CH2Cl2 was found to be similar to that of 2.2CH3CN despite the presence of different anions and solvent molecules. Powder X-ray diffraction was used to investigate the nature of bulk preparations of compounds 1-3.     

Synthese und Kristallstrukturen der Phosphanimin-Komplexe MCl2(Me3SiNPMe3)2 mit M = Zn und Co,und CoCl2(HNPMe3)2

Syntheses and Crystal Structures of the Phosphaneimine Complexes MCl₂(Me₃SiNPMe₃)₂ with M = Zn and Co, and CoCl₂(HNPMe₃)₂ The molecular complexes MCl₂(Me₃SiNPMe₃)₂ (M = Zn, Co) have been prepared by the reaction of the dichlorides of zinc and cobalt with Me₃SiNPMe₃ in CH₃CN and CH₂Cl₂, respectively, whereas the complex CoCl₂(HNPMe₃)₂ has been prepared by the reaction of CoCl₂ with NaF in boiling acetonitrile in the presence of Me₃SiNPMe₃. All complexes were characterized by IR spectroscopy and by crystal structure determinations. The complexes MCl₂(Me₃SiNPMe₃)₂ crystallize isotypically. ZnCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at ?70°C: a = 1243.6; b = 1319.0; c = 1464.7 pm. CoCl₂(Me₃SiNPMe₃)₂: Space group P2₁2₁2₁, Z = 4, 3963 observed unique reflections, R = 0,071. Lattice dimensions at ?80°C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoCl₂(HNPMe₃)₂ · CH₂Cl₂: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at ?80°C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in which the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneimine molecules.     

含dmpzm配体的锌和镉配合物的合成、结构及性质研究

通过M(NO₃)₂(M=Zn，Cd)和二(3，5-二甲基吡唑)甲烷(dmpzm)的反应，合成了2个锌和镉配合物[M(dmpzm)₂(NO₃)][NO₃](1：M=Zn；2：M=Cd)。配合物1和2经元素分析,红外光谱表征，并经X射线单晶衍射法证实。配合物1属于正交晶系，空间群为Pca2₁，晶体学参数：a=1.625 9(3) nm，b=0.832 10(17) nm，c=2.031 1(4) nm，V=2.747 9(10) nm³，Z=4。配合物2属于正交晶系，空间群为Pca2₁，晶体学参数：a=1.674 36(15) nm，b=0.821 29(7) nm，c=2.048 01(19) nm，V=2.816 3(4) nm³，Z=4。在这2个配合物的阳离子中，金属原子分别与2个dmpzm中的4个N原子及1个NO₃^-中的2个O原子配位，形成略为畸变的八面体构型。配合物1和2的晶体中，NO₃^-的O原子与配体dmpzm中的甲基及亚甲基间存在的C-H…O氢键作用，从而形成了有趣的三维网状结构。此外，还研究了配合物1和2的荧光性质。     

N(n-Bu)(4)](2)[Pu(NO(3))(6)] and [N(n-Bu)(4)](2)[PuCl(6)]: Starting Materials To Facilitate Nonaqueous Plutonium(IV) Chemistry

The reaction of plutonium(IV) in aqueous nitric acid with tetra-n-butylammonium nitrate leads to the immediate precipitation of [N(n-Bu)(4)](2)[Pu(NO(3))(6)] (1) in high yield. The analogous reaction in HCl with tetra-n-butylammonium chloride gives [N(n-Bu)(4)](2)[PuCl(6)] (2). Both 1 and 2 are soluble in a range of organic solvents and have been characterized by single-crystal X-ray diffraction, IR spectroscopy, and solid- and solution-phase vis-near-IR spectroscopy. 1 and 2 provide facile synthetic entry routes to study plutonium(IV) ligand complexation reactions in organic solvent media under both air/moisture-stable and -sensitive conditions.     

Preparation and characterization of the argentates: [Ag[P(CF(3))(2)](2)](-), [Ag[(micro-P(CF(3))(2))M(CO)(5)](2)](-) (M = Cr, W), and [Ag[(micro-P(C(6)F(5))(2))W(CO)(5)](2)](-): X-ray crystal structure of [K(18-crown-6)][Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)

The first example of a mononuclear diphosphanidoargentate, bis[bis(trifluoromethyl)phosphanido]argentate, [Ag[P(CF(3))(2)](2)](-), is obtained via the reaction of HP(CF(3))(2) with [Ag(CN)(2)](-) and isolated as its [K(18-crown-6)] salt. When the cyclic phosphane (PCF(3))(4) is reacted with a slight excess of [K(18-crown-6)][Ag[P(CF(3))(2)](2)], selective insertion of one PCF(3) unit into each silver phosphorus bond is observed, which on the basis of NMR spectroscopic evidence suggests the [Ag[P(CF(3))P(CF(3))(2)](2)](-) ion. On treatment of the phosphane complexes [M(CO)(5)PH(CF(3))(2)] (M = Cr, W) with [K(18-crown-6)][Ag(CN)(2)], the analogous trinuclear argentates, [Ag[(micro-P(CF(3))(2))M(CO)(5)](2)](-), are formed. The chromium compound [K(18-crown-6)][Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)] crystallizes in a noncentrosymmetric space group Fdd2 (No. 43), a = 2970.2(6) pm, b = 1584.5(3) pm, c = 1787.0(4), V = 8.410(3) nm(3), Z = 8. The C(2) symmetric anion, [Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)](-), shows a nearly linear arrangement of the P-Ag-P unit. Although the bis(pentafluorophenyl)phosphanido compound [Ag[P(C(6)F(5))(2)](2)](-) has not been obtained so far, the synthesis of its trinuclear counterpart, [K(18-crown-6)][Ag[(micro-P(C(6)F(5))(2))W(CO)(5)](2)], was successful.     

The Diammoniates of dipotassiumtetraethinylozincate and -cadmate: K2M(C2H)4.2NH3 (M = Zn, Cd)

By reaction of KC(2)H and K(2)Zn(CN)(4) in liquid ammonia, the diammoniate K(2)Zn(C(2)H)(4).2NH(3) was obtained. K(2)Cd(C(2)H)(4).2NH(3) was synthesized by reacting KC(2)H, Cd(NH(2))(2), and acetylene in liquid ammonia. The crystal structures of the air and temperature sensitive compounds were determined by X-ray single crystal diffraction at low temperatures (T = 170 K). Both compounds crystallize in the monoclinic space group I2/a (No. 15) with Z = 4. K(2)Zn(C(2)H)(4).2NH(3): a = 7.289(1) A, b = 12.765(2) A, c = 14.066(2) A, beta = 98.11(2) degrees. K(2)Cd(C(2)H)(4).2NH(3): a = 7.444(1) A, b = 12.619(3) A, c = 14.304(2) A, beta = 98.94(1) degrees. Characteristic structural motifs are tetrahedral [M(C(2)H)(4)](2-) fragments (M = Zn, Cd) and zigzag chains of edge sharing distorted (C(2)H)(6) octahedra centered by potassium ions. These zigzag chains are connected by a second type of crystallographically distinct potassium ions that also bind to two ammonia molecules.     

Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

The zirconium nitrate complexes (NO₂)[Zr(NO₃)₃(H₂O)₃]₂(NO₃)₃ (1), Cs[Zr(NO₃)₅] ((2), (NH₄)[Zr(NO₃)₅](HNO₃) (3), and (NO₂)_0.23(NO)_0.77[Zr(NO₃)₅] ((4) were prepared by crystallization from nitric acid solutions in the presence of H₂SO₄ or P₂O₅. The complexes were characterized by X-ray diffraction. The crystal structure of 1 consists of nitrate anions, nitronium cations, and [Zr(NO₃)₃(H₂O)₃]⁺ complex cations in which the Zr^IV atom is coordinated by three water molecules and three bidentate nitrate groups. The coordination polyhedron of the Zr^IV atom is a tricapped trigonal prism formed by nine oxygen atoms. The island structures of 2 and 3 contain [Zr(NO₃)₅]^? anions and Cs⁺ or NH₄ ⁺ cations, respectively. In addition, complex 3 contains HNO₃ molecules. Complex 4 differs from (NO₂)[Zr(NO₃)₅] in that three-fourth of the nitronium cations in 4 are replaced by nitrosonium cations NO⁺, resulting in a decrease in the unit cell parameters. In the [Zr(NO₃)₅]^? anion involved in complexes 2–4, the Zr^IV atom is coordinated by five bidentate nitrate groups and has an unusually high coordination number of 10. The coordination polyhedron is a bicapped square antiprism.     

Expanding the remarkable structural diversity of uranyl tellurites: hydrothermal preparation and structures of K[UO(2)Te(2)O(5)(OH)], Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O,beta-Tl(2)[UO(2)(TeO(3))(2)], and Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2)

The reactions of UO(2)(C(2)H(3)O(2))(2).2H(2)O with K(2)TeO(3).H(2)O, Na(2)TeO(3) and TlCl, or Na(2)TeO(3) and Sr(OH)(2).8H(2)O under mild hydrothermal conditions yield K[UO(2)Te(2)O(5)(OH)] (1), Tl(3)[(UO(2))(2)[Te(2)O(5)(OH)](Te(2)O(6))].2H(2)O (2) and beta-Tl(2)[UO(2)(TeO(3))(2)] (3), or Sr(3)[UO(2)(TeO(3))(2)](TeO(3))(2) (4), respectively. The structure of 1 consists of tetragonal bipyramidal U(VI) centers that are bound by terminal oxo groups and tellurite anions. These UO(6) units span between one-dimensional chains of corner-sharing, square pyramidal TeO(4) polyhedra to create two-dimensional layers. Alternating corner-shared oxygen atoms in the tellurium oxide chains are protonated to create short/long bonding patterns. The one-dimensional chains of corner-sharing TeO(4) units found in 1 are also present in 2. However, in 2 there are two distinct chains present, one where alternating corner-shared oxygen atoms are protonated, and one where the chains are unprotonated. The uranyl moieties in 2 are bound by five oxygen atoms from the tellurite chains to create seven-coordinate pentagonal bipyramidal U(VI). The structures of 3 and 4 both contain one-dimensional [UO(2)(TeO(3))(2)](2-) chains constructed from tetragonal bipyramidal U(VI) centers that are bridged by tellurite anions. The chains differ between 3 and 4 in that all of the pyramidal tellurite anions in 3 have the same orientation, whereas the tellurite anions in 4 have opposite orientations on each side of the chain. In 4, there are also additional isolated TeO(3)(2-) anions present. Crystallographic data: 1, orthorhombic, space group Cmcm, a = 7.9993(5) A, b = 8.7416(6) A, c = 11.4413(8) A, Z = 4; 2, orthorhombic, space group Pbam, a = 10.0623(8) A, b = 23.024(2) A, c = 7.9389(6) A, Z = 4; 3, monoclinic, space group P2(1)/n, a = 5.4766(4) A, b = 8.2348(6) A, c = 20.849(3) A, beta = 92.329(1) degrees, Z = 4; 4, monoclinic, space group C2/c, a = 20.546(1) A, b = 5.6571(3) A, c = 13.0979(8) A, beta = 94.416(1) degrees, Z = 4.     

Organometallic Fluorides of Zirconium and Hafnium in the Synthesis of Carboxylate Complexes: Molecular Structures of [{(eta(5)-C(5)Me(5))ZrF(OCOCF(3))(2)}(2)] and [(eta(5)-C(5)Me(5))(2)Zr(OCOCF(3))(2)

The reaction of [(eta(5)-C(5)Me(5))ZrF(3)] and [(eta(5)-C(5)Me(5))HfF(3)] with Me(3)SiOCOCF(3) yields the dinuclear complexes [{(eta(5)-C(5)Me(5))ZrF(OCOCF(3))(2)}(2)] (1) and [{(eta(5)-C(5)Me(5))HfF(OCOCF(3))(2)}(2)] (2), regardless of the molar ratio employed. [(eta(5)-C(5)Me(5))(2)ZrF(2)] reacts with 1 and 2 equiv of Me(3)SiOCOCF(3) to form the mononuclear compounds [(eta(5)-C(5)Me(5))(2)Zr(OCOCF(3))(2)] (3) and [(eta(5)-C(5)Me(5))(2)ZrF(OCOCF(3))] (4), respectively. The molecular structures of 1 and 3 have been determined by single-crystal X-ray analysis: 1, triclinic, P&onemacr;, a = 9.508(3) ?, b = 11.002(4) ?, c = 17.528(3) ?, alpha = 78.55(4), beta = 76.80(2), gamma = 87.51(2) degrees, V = 1750(1) ?(3), Z = 2, R = 0.0378; 3, monoclinic, C2/c, a = 18.553(4) ?, b = 9.110(2) ?, c = 16.323(3) ?, beta = 114.88(3) degrees, V = 2503(1) ?(3), Z = 4, R = 0.0457. Compound 1 shows bridging bidentate and chelating carboxylate ligands as well as bridging fluorine atoms. The zirconium atoms are seven coordinated and have an 18-electron configuration. X-ray studies of 3 reveal two structural components where the carboxylate ligands coordinate in a monodentate (major component) and a chelating manner (minor component).     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

Synthesis, Structure, and Reactivities of [eta(2)-P(7)M(CO)(4)](3)(-), [eta(2)-HP(7)M(CO)(4)](2)(-), and [eta(2)-RP(7)M(CO)(4)](2)(-) Zintl Ion Complexes Where M = Mo, W

Ethylenediamine (en) solutions of [eta(4)-P(7)M(CO)(3)](3)(-) ions [M = W (1a), Mo (1b)] react under one atmosphere of CO to form microcrystalline yellow powders of [eta(2)-P(7)M(CO)(4)](3)(-) complexes [M = W (4a), Mo (4b)]. Compounds 4 are unstable, losing CO to re-form 1, but are highly nucleophilic and basic. They are protonated with methanol in en solvent giving [eta(2)-HP(7)M(CO)(4)](2)(-) ions (5) and are alkylated with R(4)N(+) salts in en solutions to give [eta(2)-RP(7)M(CO)(4)](2)(-) complexes (6) in good yields (R = alkyl). Compounds 5 and 6 can also be prepared by carbonylations of the [eta(4)-HP(7)M(CO)(3)](2)(-) (3) and [eta(4)-RP(7)M(CO)(3)](2)(-) (2) precursors, respectively. The carbonylations of 1-3 to form 4-6 require a change from eta(4)- to eta(2)-coordination of the P(7) cages in order to maintain 18-electron configurations at the metal centers. Comparative protonation/deprotonation studies show 4 to be more basic than 1. The compounds were characterized by IR and (1)H, (13)C, and (31)P NMR spectroscopic studies and microanalysis where appropriate. The [K(2,2,2-crypt)](+) salts of 5 were characterized by single crystal X-ray diffraction. For 5, the M-P bonds are very long (2.71(1) ?, average). The P(7)(3)(-) cages of 5 are not displaced by dppe. The P(7) cages in 4-6 have nortricyclane-like structures in contrast to the norbornadiene-type geometries observed for 1-3. (31)P NMR spectroscopic studies for 5-6 show C(1) symmetry in solution (seven inequivalent phosphorus nuclei), consistent with the structural studies for 5, and C(s)() symmetry for 4 (five phosphorus nuclei in a 2:2:1:1:1 ratio). Crystallographic data for [K(2,2,2-crypt)](2)[eta(2)-HP(7)W(CO)(4)].en: monoclinic, space group C2/c, a = 23.067(20) ?, b = 12.6931(13) ?, c = 21.433(2) ?, beta = 90.758(7) degrees, V = 6274.9(10) ?(3), Z = 4, R(F) = 0.0573, R(w)(F(2)) = 0.1409. For [K(2,2,2-crypt)](2)[eta(2)-HP(7)Mo(CO)(4)].en: monoclinic, space group C2/c, a = 22.848(2) ?, b = 12.528(2) ?, c = 21.460(2) ?, beta = 91.412(12) degrees, V = 6140.9(12) ?(3), Z = 4, R(F) = 0.0681, R(w)(F(2)) = 0.1399.     

Unusual coordination modes of arylthiolates in Mo(eta(5)-SC(6)H(3)-2,6-(SiMe(3))(2))(eta(7)-SC(6)H(3)-2,6-(SiMe(3))(2))

Treatment of MoCl(3)(thf)(3) with LiSC(6)H(3)-2,6-(SiMe(3))(2) (LiSAr) resulted in formation of the pi-sandwiched bis-arylthiolato complex, Mo(eta(5)-SC(6)H(3)-2,6-(SiMe(3))(2))(eta(7)-SC(6)H(3)-2,6-(SiMe(3))(2)) (1), while the analogous reaction with LiSC(6)H(3)-2-Ph-6-SiMe(3) afforded the trithiolate complex Mo(SC(6)H(3)-2-Ph-6-SiMe(3))(3) (3). The acetonitrile adduct Mo(SAr)(2)(CH(3)CN)(3) (2) was isolated from the CH(3)CN solution of 1, in which one acetonitrile is coordinated to the metal center in an eta(2)-fashion. Structures of 1, 2, and 3 have been determined by X-ray diffraction.     

Heterodinuclear cryptates [EuML(dmf)](ClO(4))(2)(M=Ca,Cd, Ni,Zn): tuning the luminescence of europium(III) through the selection of the second metal ion

Four heterodinuclear cryptates [EuML(dmf)](ClO(4))(2) (M=Ca, Cd, Ni, Zn) were synthesized by a two-step method (L denotes deprotonated anionic cryptand synthesized by condensation of tris(2-aminoethyl)amine with 2,6-diformyl-4-chlorophenol). The ES-MS spectra of the four cryptates and the crystal structure of [EuNiL(dmf)](ClO(4))(2) x MeCN confirm that a strict dinuclear Eu(III)-M(II) entity exits in the cryptates. The cyclic voltammetry and luminescence spectral investigations indicate that the introduction of second metal ions into the mononuclear Eu(III) cryptate result in a negative shift of the redox potential of Eu(III) and a change in luminescence intensity of Eu(III). The cryptate [EuML(dmf)](ClO(4))(2) was shown to quench the emission of Eu(III) when M=Ni and to enhance the emission of Eu(III) when M=Ca, Cd, and Zn in the sequence: mononuclear相似文献   

Syntheses,reactivity, and crystal structures of molybdenum complexes with pyridine-2-thionate (pyS)-containing ligands: crystal structures of [Mo(eta(3)-C(3)H(5))(CO)(2)](2)(mu-eta(1),eta(2)-pyS)(2), exo-[Mo(eta(3)-C(3)H(5))(CO)(eta(2)-pyS)(eta(2)-dppe)], [Mo(CO)(3)(eta(1)-SC(5)H(4)NH)(eta(2)-dppm)], and [Mo(CO)(eta(2)-pyS)(2)(eta(2)-dppm)

The doubly bridged pyridine-2-thionate (pyS) dimolybdenum complex [Mo(eta(3)-C(3)H(5))(CO)(2)](2)(mu-eta(1),eta(2)-pyS)(2) (1) is accessible by the reaction of [Mo(eta(3)-C(3)H(5))(CO)(2)(CH(3)CN)(2)Br] with pySK in methanol at room temperature. Complex 1 reacts with piperidine in acetonitrile to give the complex [Mo(eta(3)-C(3)H(5))(CO)(2)(eta(2)-pyS)(C(5)H(10)NH)] (2). Treatment of 1 with 1,10-phenanthroline (phen) results in the formation of complex [Mo(eta(3)-C(3)H(5))(CO)(2)(eta(1)-pyS)(phen)] (3), in which the pyS ligand is coordinated to Mo through the sulfur atom. Four conformational isomers, endo,exo-complexes [Mo(eta(3)-C(3)H(5))(CO)(eta(2)-pyS)(eta(2)-diphos)] (diphos = dppm, 4a-4d; dppe, 5a-5d), are accessible by the reactions of 1 with dppm and dppe in refluxing acetonitrile. Homonuclear shift-correlated 2-D (31)P((1)H)-(31)P((1)H) NMR experiments of the mixtures 4a-4d have been employed to elucidate the four stereoisomers. The reaction of 4 and pySK or [Mo(CO)(3)(eta(1)-SC(5)H(4)NH)(eta(2)-dppm)] (6) and O(2) affords allyl-displaced seven-coordinate bis(pyridine-2-thionate) complex [Mo(CO)(eta(2)-pyS)(2)(eta(2)-dppm)] (7). All of the complexes are identified by spectroscopic methods, and complexes 1, 5d, 6, and 7 are determined by single-crystal X-ray diffraction. Complexes 1 and 5d crystallize in the orthorhombic space groups Pbcn and Pbca with Z = 4 and 8, respectively, whereas 6 belongs to the monoclinic space group C2/c with Z = 8 and 7 belongs to the triclinic space group Ponemacr; with Z = 2. The cell dimensions are as follows: for 1, a = 8.3128(1) A, b = 16.1704(2) A, c = 16.6140(2) A; for 5d, a = 17.8309(10) A, b = 17.3324(10) A, c = 20.3716(11) A; for 6, a = 18.618(4) A, b = 16.062(2) A, c = 27.456(6) A, beta = 96.31(3) degrees; for 7, a = 9.1660(2) A, b = 12.0854(3) A, c = 15.9478(4) A, alpha = 78.4811(10) degrees, beta = 80.3894(10) degrees, gamma = 68.7089(11) degrees.     

Estimation of coordination bond energies of NH3, H2O and Et2NH ligands in the Ni(II) and Cu(II) complexes

Tridentate ligands 2-hydroxyphenylsalicylaldimine (SAPH₂), 2-hydroxyphenyl-2-hydroxy-1-naphtalaldimine (NAPH₂) and Ni(II) complexes with multidentate ligand Bis-N·N′-(salicylidene)-1,3-propanediamine (LH₂) as well as mononuclear complex of Cu(II) were prepared using the same multidentate ligand. Diethylamine (Et₂NH), NH₃ and H₂O monodentate ligands were bound to these complexes coordinatively. The heat absorbed at the temperatures where these ligands thermally dissociated from the complexes were measured using the TG and DSC methods. It is assumed that the states both of the complexes with and without the monodentate ligands are solid and coordination bond energy for the monodentate ligand is calculated. It is seen that these calculated coordination bond energies are comparable with hydrogen bond energies.