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1.
Ulrike Riese Naim Faza Werner Massa Kurt Dehnicke 《Angewandte Chemie (International ed. in English)》1999,38(4):528-531
Unusual, highly symmetrical cubes are formed by the dodecameric cationic phosphoraneiminato complexes of copper(I ) and silver(I ) [M12(NPEt3)8]4+, in which the metal atoms occupy the edges and the N atoms of NPEt 3−3 groups the corners of the cube (see figure). The structures can be understood as molecular sections of the Cu3N structure, which is inverse to the ReO3‐type structure. 相似文献
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Hartmut Ackermann Gerd Seybert Werner Massa Oliver Bock Ulrich Müller Kurt Dehnicke 《无机化学与普通化学杂志》2000,626(12):2463-2466
[Ag12F(NPEt3)8]3+: A Metalla‐Cryptand filled with a Fluoride Ion [Ag12F(NPEt3)8](SiF6)1,5 ( 1 ) was obtained from the reaction of silver(I) fluoride with the silylated phosphaneimine Me3SiNPEt3 in acetonitrile. It forms colorless, light‐ and hydrolysis‐sensitive crystals, which incorporate acetonitrile that is lost in vacuo. 1 · 2,4 CH3CN was characterized by its IR spectrum and by X‐ray crystal structure analysis. Space group Pa 3, Z = 8, a = 2734.8(1) pm at 153 K, R = 0.059. The compound consists of cations [Ag12F(NPEt3)8]3+ (point group C3), SiF62– counter‐ions and acetonitrile molecules which show no interactions. In the cation the silver atoms are located on the edges of a nearly undistorted cube and the N atoms of the phosphoraneiminato groups (NPEt3–) occupy the vertices. A fluoride ion in the center of the cube has contacts of nearly similar length to the 12 silver atoms (mean distance 304.7 pm). 相似文献
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Soheila Chitsaz Kurt Dehnicke Gerlinde Frenzen Astried Pilz Ulrich Müller 《无机化学与普通化学杂志》1996,622(12):2016-2022
Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SbF2(NPEt3)]2 and [SbF(NPEt3)2]2 as well as of NMe4+SbF4? The title compounds have been prepared from antimony trifluoride with the silylated phosphaneimine Me3SiNPEt3 and [NMe4]F, respectively. They were characterized by IR spectroscopy and by crystal structure determinations. [SbF2(NPEt3)]2 : Space group Pbca, Z = 8, structure determination with 1264 unique reflections, R1 = 0.028 for reflections with I > 2σ(I). Lattice dimensions at ?80°C: a = 1284.8, b = 1162.4, c = 1380.4 pm. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ2-N bridges of the NPEt3? ligands. [SbF(NPEt3)2]2 : Space group P21/c, Z = 4, structure determination with 2270 unique reflections, R1 = 0.029 for reflections with I > 2μ(I). Lattice dimensions at ?75°C: a = 815.8, b = 1121.2, c = 2068.5 pm, β = 101.09°. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ2-N bridges of one of the two NPEt3? ligands. The other NPEt3? group is terminally connected. NMe4+SbF4? : Space group P21/c, Z = 4, structure determination with 1503 unique reflections, R1 = 0.069 for reflections with I > 2μ(I). Lattice dimensions at ?50°C: a = 539.80, b = 896.10, c = 1760.3 pm, β = 90.338°. The compound includes monomeric SbF4? ions with distorted Ψ-trigonal-bipyramidal environment of the antimony atoms. 相似文献
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Phosphoraneiminato Complexes of Titanium(IV). Crystal Structures of [TiCl3(NPEt3)]2, [TiCl3(NPEt3)(THF)2], and [TiCl4{Me2Si(NPEt3)2}] [TiCl3(NPEt3)]2 ( 1 ) is formed from titanium(IV) chloride and the silylated phosphaneimine Me3SiNPEt3 in dichloromethane as reddish-brown, moisture-sensitive crystals. According to the crystal structure analysis these crystals show centrosymmetric Ti2N2 four-membered rings with Ti–N distances of 184.7 and 210.3 pm. With tetrahydrofurane 1 forms yellow, moisture sensitive crystals of the solvate [TiCl3(NPEt3)(THF)2] ( 2 ), in which the titanium atom is octahedrally coordinated. The THF molecule which is in trans position to the phosporaneiminato ligand realizes but a very weak Ti–O bond of 238.0 pm, the cis THF molecule shows a Ti–O distance of 213.7 pm. With 173.4 pm along with a TiNP bond angle of 160.0° the TiN distance is very short. The bis(phosphaneimine) complex [TiCl4{Me2Si(NPEt3)2}] ( 3 ) is formed as colourless crystals in low yield in the reaction of titanium(IV) chloride with Me3SiNPEt3 and trimethylcyclopentadienylsilane. In 3 the titanium atom is surrounded by four chlorine atoms in a distorted octahedral fashion and by the two N atoms of the Me2Si(NPEt3)2 molecule with TiN distances of 205.6 pm. 相似文献
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[(HBNPEt3)4NPEt3]3+ – a Bicyclic Penta(phosphorano)borazinium Trication [(HBNPEt3)4NPEt3]Br3 ( 1 ) has been prepared by the reaction of Me3SiNPEt3 with [HBBr2(SMe2)] in dichloromethane solution at 20°C. According to 11B‐NMR and 31P‐NMR spectroscopy and to a crystal structure determination the cation of 1 has the structure of a bicyclic penta(phosphorano)borazinium‐trication. 1 _.3CH2Cl2: Space group P212121, Z = 8, lattice dimensions at –83°C: a = 2124.8(1), b = 2307.6(1), c = 2323,1(1) pm, R1 = 0.0733. 相似文献
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Phosphoraneiminato Acetate Cluster of Copper and Zinc. Crystal Structures of [Cu4(NPEt3)2(O2CCH3)6] and [Zn4(NPEt3)2(O2CCH3)6] The anhydrous acetates of copper(II) and zinc react with the silylated phosphaneimine Me3SiNPEt3 in dichloromethane at 20 °C forming the mixed phosphoraneiminato acetate clusters [Cu4(NPEt3)2(O2CCH3)6] ( 1 ), which forms emerald crystals, and colourless [Zn4(NPEt3)2 · (O2CCH3)6] ( 2 ). In spite of analogous composition the structures of 1 and 2 are completely different. In the asymmetric unit of 1 three copper atoms of an almost isosceles triangle are linked via two nitrogen atoms of the NPEt3– groups to form a trigonal bipyramidal aggregate. One of these three copper atoms is chelated by an acetate group, another one is connected with the fourth copper atom via three μ2‐O2C–CH3 groups. The asymmetric units are associated via a μ2‐O2C–CH3 group and a μ3‐OC(O)CH3 group at a time so that infinite chains result. In 2 two zinc atoms are linked via the nitrogen atoms of the two NPEt3– groups to form an almost centrosymmetric four‐membered ring. Both nitrogen atoms of the four‐membered ring are connected with another zinc atom each. These zinc atoms again are linked with the zinc atoms of the Zn2N2 four‐membered ring via two μ2‐O2C–CH3 groups each and additionally coordinated with a terminal acetate ligand each. 相似文献
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Kalinina I. V. Pervukhina N. V. Podberezskaya N. V. Fedin V. P. 《Russian Journal of Coordination Chemistry》2002,28(6):389-393
Single crystals of [Zn(NH3)4]3[Mo4Te4(CN)12] (I) and [Cd(NH3)4]3[W4Te4(CN)12] (II) were obtained by applying solutions of K7[Mo4Te4(CN)12] · 11H2O and K6[W4Te4(CN)12] · 5H2O in aqueous ammonia over solutions of ZnCl2 and Cd(NO3)2 in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined. 相似文献
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Phosphoraneiminato Cluster of Iron. The Crystal Structures of [FeCl(NPEt3)]4, [Fe(C=C–SiMe3)(NPEt3)]4, and [Fe3Cl4{NP(NMe2)3}3] The reaction of iron dichloride with the silylated phosphaneimine Me3SiNPEt3 in the presence of potassium fluoride at 165 ?C leads to the phosphoraneiminato complex [FeCl(NPEt3)]4 ( 1 ). Compound 1 forms black, moisture and oxygen sensitive crystals. According to the crystal structure analysis 1 has a heterocubane structure, in which the iron and the nitrogen atoms of the NPEt3– groups occupy the corners of a distorted cube and form Fe–N–Fe bond angles of 83.1? and N–Fe–N angles of 96.5?. This results in significantly short Fe…Fe contacts of 272.9 pm. The results of magnetic susceptibility measurements in the range of temperatures from 1.8 to 293 K and the 57Fe‐Mössbauer spectra in the range of temperatures from 2 to 300 K are reported. Compound 1 reacts with the lithiated acetylenes LiC=C–CMe3 and LiC=C–SiMe3 in n‐hexane to form the iron‐organic derivatives [Fe(C=C–R)(NPEt3)]4 [R = CMe3 ( 2 a ), R = SiMe3 ( 2 b )] keeping the heterocubane structure. Compounds 2 a and 2 b form crystals which are very reactive and also black. According to the crystal structure analysis 2 b has a Fe4N4 heterocubane structure which is less distorted than that in 1 with bond angles Fe–N–Fe of 85.5? and N–Fe–N of 94.2?. This leads to the longer Fe…Fe contacts of 281.4 pm. With the dimethylamido derivative Me3SiNP(NMe2)3 iron dichloride reacts under conditions similar to those in the synthesis of 1 to form the dark green mixed‐valenced FeII/FeIII cluster [Fe3Cl4{NP(NMe2)3}3] ( 3 ). According to the crystal structure analysis the three iron atoms in 3 are connected via one μ3‐N atom of a NP(NMe2)3– ligand, via two μ‐N atoms of the two remaining phosphoraneiminato ligands, and via one μ‐Cl atom to form an incomplete heterocubane skeleton. 相似文献
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Fluorination of [Os(3)CO(12)] in HF/SbF(5) affords [Os(CO)(4)(FSbF(5))(2)]. According to its crystal structure (orthorhombic, Pna2(1), a = 1590.3(3), b = 1036.6(1), c = 878.2(2) pm, Z = 4), the two SbF(6) units occupy cis positions in the octahedral environment around the Os atom. Fluorination of [Ir(4)(CO)(12)] in HF/SbF(5) produced three different compounds: (1) [Ir(4)(CO)(8)(mu-F)(2)(Sb(2)F(11))(2)] (tetragonal, P4n2, a = 1285.2(2), c = 952.9(1) pm, Z = 2). Here, two of the six edges of the Ir(4) tetrahedron in [Ir(4)CO(12)] are replaced by bridging fluorine atoms. (2) [fac-Ir(CO)(3)(FSbF(5))(2)HF]SbF(6).HF (orthorhombic, Pnma, a = 1250.6(1), b = 1340.7(2), c = 1092.6(2) ppm, Z = 4). The Ir(4) tetrahedron in Ir(4)(CO)(12) is completely broken down, but the facial Ir(CO)(3) configuration is retained. (3) [mer-Ir(CO)(3)F(FSbF(5))(2)] (triclinic, P1, a = 834.9(1), b = 86 4.9(1), c = 1060.0(1) pm, alpha = 69.173(4) degrees, beta = 77.139(4) degrees, gamma = 88.856(4) degrees, Z = 2). 相似文献
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Phosphoraneiminato Complexes of Boron. Syntheses and Crystal Structures of [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 and [{B2(NMe2)2}2(NPEt3)2]Cl The bromoderivatives of the title compounds are prepared from the corresponding silylated phosphoraneimines Me3SiNPR3 and boron tribromide. The boron subcompound [{B2(NMe2)2}2(NPEt3)2]Cl2 derives from Me3SiNPEt3 and B2Cl2(NMe2)2. All complexes are characterized by NMR and IR spectroscopy as well as by crystal structure determinations. [BBr2(NPMe3)]2 (1): Space group P21/n, Z = 2, R = 0.031. Lattice dimensions at ?50°C: a = 723.8, b = 894.2, c = 1305.4 pm, β = 92.35°. 1 forms centrosymmetric molecules in which the boron atoms are linked via μ2-N bridges of the NPMe3? groups of from B2N2 four-membered rings with B? N distances of 149.9 and 150.9 pm. B2Br3(NPiPr3)2]Br (2): Space group P21, Z = 2, R = 0.059. Lattice dimensions at ?80°C: a = 817.6, b = 2198.7, c = 851.5 pm, β = 115.09°. In the cations of 2 the boron atoms are lined via the μ2-N atoms of the NPiPr3? groups to form planar, asymmetric B2N2 four-membered rings with B? N distances of 143 and 156 pm. [B2(NPEt3)4[Br2·4CH2Cl2 (3): Space group C2/c, Z = 4, R = 0.042. Lattice dimensions at ?50°C: a = 1946.1, b = 1180.3, c = 2311.3 pm, β = 101.02°. The structure contains centrosymmetric dications in which both the boron atoms are lined by the N atoms of two of the NPEt3? groups to form a B2N2 four-membered ring with B? N distances of 149.6 pm. The remaining two NPEt3? groups are terminally bonded with very short B? N distances of 133.5 pm. B2Br2(NPPh3)3]BBr4 (4): Space group P1 , Z = 2, R = 0.065. Lattice dimension at ?50°C: a = 1025.7, b = 1496.1, c = 1807.0 pm, α = 85.09°, β = 82.90°, γ = 82.72°. In the cation the boron atoms are lined via the μ2-N atoms of two of the NPPh3? groups to form a nearly planer B2N2 four-membered ring with B? N distances of 149.3-153.1 pm. The third NPPh33 group is terminally connected with teh sp2 hybridized boron atom and with a B? N distance of 134.1 pm along with an almost linear BNP bond angle of 173.6°. [{B2(NMe2)2}2(NPEt2)2]Cl2 · 3CH2Cl2 (5): Space group C2/c, Z = 4, R = 0.098. Lattice dimensions at ?70°C: a = 1557.9, b = 1294.7, c = 2122.9 pm, β = 96.08°. The structure of 4 contains centrosymmetric dications in which two by two B-B dumb-bells are linked via the μ2-N atoms of the two NEPt3? groups to form B4N2 six-membered rings with B? N distances of 150 and 156 pm and B-B distances of 173 pm. The B? N distances of the terminally bonded NMe2? groups correspond to 138 pm double bonds. 相似文献
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Three Novel Selenoborato- closo -dodecaborates: Syntheses and Crystal Structures of Rb8[B12(BSe3)6], Rb4Hg2[B12(BSe3)6], and Cs4Hg2[B12(BSe3)6] The three selenoborates Rb8[B12(BSe3)6] (P1, a = 10.512(5) Å, b = 10.450(3) Å, c = 10.946(4) Å, α = 104.53(3)°, β = 91.16(3)°, γ = 109.11(3)°, Z = 1), Cs4Hg2[B12(BSe3)6] (P1, a = 9.860(2) Å, b = 10.740(2) Å, c = 11.078(2) Å, α = 99.94(3)°, β = 90.81(3)°, γ = 115.97(3)°, Z = 1), and Rb4Hg2[B12(BSe3)6] (P1, a = 9.593(2) Å, b = 10.458(2) Å, c = 11.131(2) Å, α = 99.25(3)°, β = 91.16(3)°, γ = 116.30(3)°, Z = 1) were prepared from the metal selenides, amorphous boron and selenium by solid state reactions at 700 °C. These new chalcogenoborates contain B12 icosahedra completely saturated with six trigonal-planar BSe3 entities functioning as bidentate ligands to form a persubstituted closo-dodecaborate anion. The two isotypic compounds Rb4Hg2[B12(BSe3)6] and Cs4Hg2[B12(BSe3)6] are the first selenoborate structures containing a transition metal which are characterized by single crystal diffraction. 相似文献
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Tetramethyl Ammonium Amalgam, [N(CH3)4]Hg8 Crystals of tetramethyl ammonium amalgam with the composition [N(CH3)4]Hg8 were prepared by electrolysis. According to temperature‐dependent X‐ray diffraction experiments the compound transforms into an amorphous product above 6 °C; the decomposition is a multi‐stage process as shown by DTA experiments. X‐ray examinations of crystalline aggregates indicate a structure of low symmetry with remarkable similarities to that of α‐Hg. 相似文献
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Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr, Ph), and [Zn10Te4(TePh)12(PR3)2] (R = nPr, Ph) In the prescence of NEt4Cl ZnCl2 reacts with PhSeSiMe3 or a mixture of PhSeSiMe3/Se(SiMe3)2 to form the ionic complexes [NEt4]2[Zn4Cl4(SePh)6] 1 or [NEt4]2[Zn8Cl4Se(SePh)12] 2 respectively. The use of PnPr3 instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn8Se(SePh)14(PnPr3)2] 3 . Reactions of ZnCl2 with PhTeSiMe3 and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr 4 , Ph 5 ) and in THF of the uncharged [Zn10Te4(TePh)12(PR3)2] (R = nPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P21/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P21/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P21/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P21/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I41/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°) 相似文献
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Xu Z Wang Q Li H Meng W Han Y Hou H Fan Y 《Chemical communications (Cambridge, England)》2012,48(46):5736-5738
[8+12]-metallamacrocycle-based 3D frameworks {[Cu(4)(pbt)(2)(SO(4))(2)(DMF)(2)(CH(3)OH)]·7H(2)O·DMF}(n) (1) and [12]-macrocycle 3D {[Cu(2)(pbt)(SO(4))(DMSO)(CH(3)OH)(2)]·5H(2)O·CH(3)OH}(n) (2) have been obtained. Both complexes display antiferromagnetic couplings and high catalytic activity in the oxidative coupling reaction of 1-ethynylbenzene and oxazolidin-2-one. 相似文献
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