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1.
[ScCl2{N(SiMe3)2}(THF)2] – a Precursor for the Synthesis of Scandium Nitride [ScCl2{N(SiMe3)2}(THF)2] ( 1 ) has been prepared by the reaction of [ScCl3(THF)3] with the trisamide Sc[N(SiMe3)2]3 in tetrahydrofurane solution forming colourless moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P 1, Z = 2, lattice dimensions at –50 °C: a = 841.4(1), b = 924.2(1), c = 1550.0(1) pm, α = 90.046(7)°, β = 95.671(9)°, γ = 106.066(6)°, R1 = 0.0329. In the molecular structure of 1 the scandium atom has a distorted trigonal‐bipyramidal coordination with the THF molecules in apical positions. At 400 °C 1 is converted into scandium nitride, ScN, by stepwise leaving of THF and ClSiMe3.  相似文献   

2.
Crystal Structures of a Series of Compounds with Cations of the Type [R3PNH2]+, [R3PN(H)SiMe3]+, and [R3PN(SiMe3)2]+ The crystal structures of a series of compounds with cations of the type [R3PNH2]+, [R3PN(H)SiMe3]+, and [R3PN(SiMe3)2]+, in which R represents various organic residues, are determined by means of X‐ray structure analyses at single crystals. The disilylated compounds [Me3PN(SiMe3)2]+I, [Et3PN(SiMe3)2]+I, and [Ph3PN(SiMe3)2]+I3 are prepared from the corresponding silylated phosphaneimines R3PNSiMe3 with Me3SiI. [Me3PNH2]Cl (1): Space group P21/n, Z = 4, lattice dimensions at –71 °C: a = 686.6(1), b = 938.8(1), c = 1124.3(1) pm; β = 103.31(1)°; R = 0.0239. [Et3PNH2]Cl (2): Space group Pbca, Z = 8, lattice dimensions at –50 °C: a = 1272.0(2), b = 1147.2(2), c = 1302.0(3) pm; R = 0.0419. [Et3PNH2]I (3): Space group P212121, Z = 4, lattice dimensions at –50 °C: a = 712.1(1), b = 1233.3(2), c = 1257.1(2) pm; R = 0.0576. [Et3PNH2]2[B10H10] (4): Space group P21/n, Z = 4, lattice dimensions at –50 °C: a = 809.3(1), b = 1703.6(1), c = 1800.1(1) pm; β = 96.34(1)°; R = 0.0533. [Ph3PNH2]ICl2 (5): Space group P1, Z = 2, lattice dimensions at –60 °C: a = 825.3(3), b = 1086.4(3), c = 1241.2(4) pm; α = 114.12(2)°, β = 104.50(2)°, γ = 93.21(2)°; R = 0.0644. In the compounds 1–5 the cations are connected with their anions via hydrogen bonds of the NH2 groups with 1–3 forming zigzag chains. [Me3PN(H)SiMe3][O3S–CF3] (6): Space group P21/c, Z = 8, lattice dimensions at –83 °C: a = 1777.1(1), b = 1173.6(1), c = 1611.4(1) pm; β = 115.389(6)°; R = 0.0332. [Et3PN(H)SiMe3]I (7): Space group P21/n, Z = 4, lattice dimensions at –70 °C: a = 1360.2(1), b = 874.2(1), c = 1462.1(1) pm; β = 115.19(1)°; R = 0.066. In 6 and 7 the cations form ion pairs with their anions via NH … X hydrogen bonds. [Me3PN(SiMe3)2]I (8): Space group P21/c, Z = 8, lattice dimensions at –60 °C: a = 1925.4(9), b = 1269.1(1), c = 1507.3(4); β = 111.79(3)°; R = 0.0581. [Et3PN(SiMe3)2]I (9): Space group Pbcn, Z = 8, lattice dimensions at –50 °C: a = 2554.0(2), b = 1322.3(1), c = 1165.3(2) pm; R = 0.037. [Ph3PN(SiMe3)2]I3 (10): Space group P21, Z = 2, lattice dimensions at –50 °C: a = 947.7(1), b = 1047.6(1), c = 1601.6(4) pm; β = 105.96(1)°; R = 0.0334. 8 to 10 are built up from separated ions.  相似文献   

3.
[Yb3OBr4{N(SiMe3)2}3(THF)3], an Amido Complex of Ytterbium with a Clusterlike Structure The title compound has been prepared from YbBr3 and NaN(SiMe3)2 in THF suspension, forming yellow single crystals from hexane solutions which were characterized by a crystal structure determination. Space group P1 , Z = 2, lattice dimensions at ?100°C: a = 1085.4(1), b = 1410.2(1), c = 1912.0(1) pm; α = 78.62(1)°, β = 80.61(1)°, γ = 73.45(1)°, R = 0.025. In the molecular structure of [Yb3OBr4{N(SiMe3)2}3(THF)3] the three ytterbium atoms together with the μ3-oxygen atom and a μ3-bromine atom form a distorted trigonal bipyramid. In addition, three μ2-Br atoms coordinate the Yb atoms in the equatorial plane, whereas the THF molecules and the N(SiMe3)2? ligands are terminally coordinated, thus forming a distorted octahedrally surrounding of the Yb atoms.  相似文献   

4.
The Reaction of Ytterbium with N‐iodo‐triphenylphosphaneimine. Crystal Structures of [Yb2I(THF)2(NPPh3)4] · 2 THF, [YbI2(HNPPh3)(DME)2], and [{YbI2(DME)2}2(μ‐DME)] When treated with ultrasound, the reaction of ytterbium powder with INPPh3 in tetrahydrofuran leads to [YbI2(THF)4] and to the mixed‐valence phosphoraneiminato complex [Yb2I(THF)2(NPPh3)4] · 2 THF ( 1 ), which forms red single‐crystals. In the analogous reaction in 1,2‐dimethoxyethane (DME) only the ytterbium(II) iodide solvates [YbI2(HNPPh3)(DME)2] ( 2 ) and [{YbI2(DME)2}2 · (μ‐DME)] ( 3 ) can be isolated, which form yellow single crystals. All compounds were characterized by crystal structure analyses. 1 : Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1337.6(5), b = 1389.6(5), c = 2244.2(17) pm; α = 86.11(7)°, β = 88.06(7)°, γ = 88.63(4)°; R = 0.0759. In 1 the two ytterbium atoms are connected via the N atoms of two phosphoraneiminato groups (NPPh3) to form a planar Yb2N2 four‐membered ring. The structure can also be described as an ion pair consisting of [YbI(THF)2]+ and [Yb(NPPh3)4]. 2 : Space group P21, Z = 2, lattice dimensions at –80 °C: a = 811.9(1), b = 1114.0(1), c = 1741.3(1) pm; β = 95.458(5)°; R = 0.0246. 2 forms molecules in which the ytterbium atom is coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions. The O atoms of the two DME‐chelates and the N atom of the phosphaneimine ligand HNPPh3 are in the equatorial positions. 3 : Space group P1, Z = 2, lattice dimensions at –70 °C: a = 817.5(1), b = 1047.7(1), c = 1115.5(2) pm; α = 90.179(10)°, β = 97.543(15)°, γ = 91.087(12)°; R = 0.0317. 3 has a dimeric molecular structure, in which the two fragments {YbI2(DME)2} are connected centrosymmetrically via a μ‐DME bridge. As in 2 , the ytterbium atoms are coordinated in a pentagonal‐bipyramidal fashion with the iodine atoms in the axial positions, as well as with the two DME chelates and with one O atom each of the μ‐DME ligand in the equatorial positions.  相似文献   

5.
A New Synthesis and the Crystal Structure of Hexaphenyl‐cyclo‐triphosphazene, [NPPh2]3 · THF [NPPh2]3 · THF ( 1 · THF) has been prepared from KNPPh3 in THF solution in the presence of MoO3 and 18‐crown‐6. According to the crystal structure determination all structural parameters are similar to known symmetric substituted cyclo‐triphosphazenes. The dihedral angles of the phenyl groups with the “best plane” P3N3 lie between 50 and 67°. 1 · THF: Space group P 1, Z = 2, lattice dimensions at –80 °C: a = 1146.5(1), b = 1360.5(1), c = 1382.9(1) pm, α = 108.06(1)°, β = 103.32(1)°, γ = 112.19(1)°, R1 = 0.0441.  相似文献   

6.
Crystal Structures of the Samarium Amido Complexes [Sm(l-X){N(SiMe3)2}2(THF)]2 with X = Cl, Br The crystal structures of the title compounds have been determined by X-ray methods. [Sm(μ-Cl) · {N(SiMe3)2}2(THF)]2 ( 1 ): Space group P21/n, Z = 2, lattice dimensions at 223 K: a = 1429.5(2), b = 1302.3(3), c = 1658.6(3) pm, β = 114.212(10)°, R = 0.0561. [Sm(μ-Br) · {N(SiMe3)2}2(THF)]2 ( 2 ): Space group Pbca, Z = 4, lattice dimensions at 223 K: a = 1850.0(7), b = 1611.0(9), c = 1888.1(6) pm, R = 0.0497. 1 and 2 form centrosymmetric dimeric complexes via μ-X-halogeno bridges. The samarium atoms are coordinated in a distorted trigonal-bipyramidal surrounding, the THF molecule and one of the bridging halogen atoms being in axial positions.  相似文献   

7.
Synthesis and Crystal Structures of the Samarium Complexes [SmI2(DME)3] and [Sm2I(NPPh3)5(DME)] When treated with ultrasound, the reaction of samarium metal with N-iodine-triphenylphosphaneimine in 1,2-dimethoxyethane (DME) leads to the two samarium complexes [SmI2(DME)3] ( 1 ) and [Sm2I(NPPh3)5(DME)] ( 2 ), which are separated from each other by fractional crystallization. 1 could be isolated in two different crystallographic forms, namely as brownish black crystals ( 1 a ) and as violet-black crystals ( 1 b ), both of them are characterized by crystal structure analyses. 1 a : Space group P21/c, Z = 4, lattice dimensions at –80 °C: a = 1459.4(1), b = 1314.4(1), c = 2293.6(2) pm, β = 99.245(8)°, R = 0.0344. The structure of 1 a holds two crystallographically independent molecules [SmI2(DME)3], in which the samarium atoms have coordination number eight. The two individuals differ from each other particularly in their I–Sm–I bond angles, which are 157.94 and 178.45°. 1 b : Space group P21, Z = 2, lattice dimensions at –80 °C: a = 849.4(3), b = 1060.1(3), c = 1235.1(6) pm, b = 93.86(5)°, R = 0.0251. 1 b has a molecular structure similar to that of 1a with a bond angle I–Sm–I of 158.40°. The phosphoraneiminato complex [Sm2I(NPPh3)5(DME)] ( 2 ) forms colourless, moisture sensitive crystals which contain two molecules DME per formula unit. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1405.0(4), b = 1656.5(3), c = 2208.3(7) pm, α = 89.60(3)°, β = 72.96(4)°, γ = 78.70(3)°, R = 0.0408. In 2 the two samarium atoms are linked via the μ-N atoms of two phosphoraneiminato ligands to form a planar Sm2N2 four-membered ring. One of the Sm atoms is terminally coordinated by the N atoms of two (NPPh3) groups, thus achieving a distorted tetrahedral surrounding. The second Sm atom is coordinated by the N atom of one (NPPh3) group, by the terminally bonded iodine atom, and by the O atoms of the DME chelate, thus achieving a distorted octahedral surrounding.  相似文献   

8.
Pyridine Complexes of Rare Earth Element Trichlorides. Syntheses and Crystal Structures of [YCl3(py)4] and [LnCl3(py)4] · 0.5 py with Ln = La and Er The pyridine complexes [YCl3(py)4] ( 1 ), [LaCl3(py)4] · 0.5 py ( 2 · 0.5 py), and [ErCl3(py)4] · 0.5 py ( 3 · 0.5 py) have been prepared from the diacetone‐alcohol complexes [LnCl3(DAA)2] or directly from the metal trichlorides with excess pyridine to give colourless, only sparingly moisture sensitive crystals. They were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group Pbca, Z = 16, lattice dimensions at –80 °C: a = 1647.4(1), b = 1743.1(1), c = 3190.5(1) pm, R1 = 0.031. 2 · 0,5 Py: Space group P21/n, Z = 4, lattice dimensions at –80 °C: a = 978.9(1), b = 1704.5(1), c = 1589.5(1) pm, β = 103.61(1)°, R1 = 0.0281. 3 · 0,5 Py: Space group P21/n, Z = 4, lattice dimensions at –80 °C: a = 970.1(1), b = 1706.4(1), c = 1566.1(1) pm, β = 103.46(1)°, R1 = 0.0232. All complexes realize monomeric molecular structures with the metal atom in a distorted pentagonal‐bipyramidal coordination. One of the chlorine atoms and the four pyridine molecules are in the equatorial plane.  相似文献   

9.
Phosphoraneiminato Complexes of Rare-Earth Elements. Crystal Structures of [Yb2Cp3(NPPh3)3], [YCp(NPPh3)(μ-OSiMe2NPPh3)]2, and [M(NPPh3)2(μ-OSiMe2NPPh3)]2 with M = Y and Sm The ytterbium complex [Yb2Cp3(NPPh3)3] with sesqui distribution of cyclopentadienide and phosphoraneiminato ligands is made from YbCp2Cl and LiNPPh3 in boiling toluene and isolated as yellow, moisture sensitive crystals, which enclose three molecules of toluene per unit cell. [Yb2Cp3(NPPh3)3] · 3 C7H8 ( 1 ): Space group Pbca, Z = 8, lattice dimensions at –80 °C: a = 2727.6(2), b = 1977.5(1), c = 2848.9(2) pm; R = 0.0541. Two of the (NPPh3)-groups link the ytterbium atoms to a nonplanar Yb2N2 four-membered ring with a folding angle of 17.1° along the Yb…Yb connecting line. The third (NPPh3) group is terminally bonded with a short Yb–N distance of 214.2 pm. [YCp(NPPh3)(μ-OSiMe2NPPh3)]2 · 4 C7H8 ( 2 ) originates from YCpCl2 and LiNPPh3 in boiling toluene with Baysilon-paste participating forming colourless, moisture sensitive crystals. Space group P21/c, Z = 2, lattice dimensions at –80 °C: a = 1469.0(1), b = 1234.1(1), c = 2761.5(2) pm, β = 93.196(10)°; R = 0.0518. In 2 the yttrium atoms are linked via the oxygen atoms of the (OSiMe2NPPh3) groups to form a centrosymmetric Y2O2 four-membered ring with Y–O bonds of different lengths. Together with the terminally bonded (NPPh3)-ligand, the η5-C5H5 group, and the N atom of the siloxyphosphaneimine group, which functions as a donor atom, the Y atoms achieve coordination number five. [Y(NPPh3)2(μ-OSiMe2NPPh3)]2 · 2 C7H8 ( 3 ) and [Sm(NPPh3)2(μ-OSiMe2NPPh3)]2 ( 4 ) originate from the metal trichlorides with KNPPh3 in THF with Baysilon paste participating and subsequent crystallization from toluene as colourless, moisture sensitive crystal needles. 3 : Space group P21/n, Z = 2, lattice dimensions at –80 °C: a = 1804.1(2), b = 1401.8(1), c = 2221.6(2) pm, β = 98.716(9)°; R = 0.0537. 4 : Space group P 1, Z = 1, lattice dimensions at –80 °C: a = 1363.4(1), b = 1364.9(1), c = 1650.6(1) pm; α = 112.457(8)°, β = 91.948(9)°, γ = 114.974(8)°; R = 0.0308. 3 and 4 form centrosymmetric dimeric molecules in which the metal atoms are linked via the oxygen atoms of the (OSiMe2NPPh3) groups to form M2O2 four-membered rings with M–O bonds of varying length. Together with the terminally bonded (NPPh3) ligands and the N atom of the siloxyphosphaneimine ligand, which functions as a donor atom, the metal atoms achieve coordination number five.  相似文献   

10.
Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI2(THF)5]+I3?, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]?, [ErCl3(DME)2], and [Na(18-Crown-6)(THF)2]+[YbBr4(THF)2]? [LaI2(THF)5]+I3? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl3(THF)4] ( 2 ) originates as colourless crystals on heating SmCl3 with excess THF in the presence of Me3SiNPEt3. Space group P21/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl2(THF)5]+[ErCl4(THF)2]? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC13(DME)2] ( 4 ) originates as pink single crystals from 3 with excess boiling 1,2-dimethoxyethane. Space group P21/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]? ( 5 ) is formed as by-product by the reaction of YbBr3 with NaN(SiMe3)2 in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr4(THF)2]?ions, in which the THF molecules are arranged in trans-position.  相似文献   

11.
Syntheses and Crystal Structures of the Phosphorane Iminato Complexes [MCl2(NPPh3)]2 with M = Al and Ga, [SbCl2(NPMe3)(DMF)]2, and of the Phosphorane Imine Complex [Ph3PNH · BF3] · THF The phosphorane iminato complexes [MCl2(NPPh3)]2 with M = Al and Ga and [SbCl2(NPMe3)(DMF)]2 are formed as colourless crystals by reactions of the anhydrous trichlorides MCl3 (M = Al, Ga, Sb) with the corresponding silylated phosphorane imines Me3SiNPR3 in acetonitrile and in dimethyl formamide, respectively. The phosphorane imine derivative [Ph3PNH · BF3] · THF is formed from Me3SiNPPh3 and boron trifluoride etherate in boiling tetrahydrofuran. The compounds are characterized by their i. r. spectra and by crystal structure analyses. [AlCl2(NPPh3)]2 : Space group P1 , Z = 1, structure solution with 1 585 observed unique reflections, R = 0.061. Lattice dimensions at ?70°C: a = 917.6, b = 1 053.5, c = 1 145.2 pm, α = 111.72°, β = 100.80°, γ = 109.95°. [GaCl2(NPPh3)]2 : Space group P1 , Z = 1, structure solution with 2 586 observed unique reflections, R = 0.066. Lattice dimensions at ?70°C: a = 917.5, b = 1 058.3, c = 1 153.7 pm, α = 105.52°, β = 107.75°, γ = 109.88°. In both compounds the metal atoms are linked to planar M2N2 four-membered rings via the N-atoms of the phosphorane iminato groups. [SbCl2(NPMe3)(DMF)]2 : Space group P21/n, Z = 4, structure solution with 3 805 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 1 913.0, b = 726.8, c = 2 040.7 pm, β = 113.62°. The unit cell contains two symmetry independent dimeric molecules, in which the antimony atoms are centrosymmetricly μ2 linked via the N-atoms of the phosphorane iminato groups. Along with the oxygen atom of the dimethyl formamide molecule the Sb atoms achieve a ψ-octahedral environment. [Ph3PNH · BF3] · THF : Space group C2/c, Z = 8, structure solution with 2 048 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 2 460.4, b = 869.2, c = 1 978.0 pm, β = 116.35°.  相似文献   

12.
Functionalized Alkyne Complexes of Tungsten(VI). Syntheses and Crystal Structures of [WCl4(Et? Se? C?C? Se? Et)(THF)] and [WCl4(Et? Te? C?C? Te? Et)(THF)] The title compounds have been prepared by reactions of [WCl4(SEt2)2] with the alkynes Et? X? C?C? X? Et (X = Se, Te) in CCl4 solution and subsequent addition of tetrahydrofurane. Both complexes were characterized by crystal structure determinations. [WCl4(Et? Se? C?C? Se? Et)(THF)]: Space group P21/n, Z = 4, structure determination with 2942 unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 934.2, b = 1639.5, c = 1189.5 pm, β = 96.497°. [WCl4(Et? Te? C?C? Te? Et)(THF)]: Space group P21/n, Z = 4, structure determination with 4097 unique reflections, R = 0.067, Lattice dimensions at ?70°C: a = 899.2, b = 1691.9, c = 1213.3 pm, β = 96.82°. The complexes have monomeric molecular structures with the oxygen atom of the THF molecules in trans-position to the side-on bound alkyne ligands.  相似文献   

13.
(PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] – a Nitrido‐Thionitrosyl‐Dinitridosulfato‐Complex of Rhenium The title compound has been prepared from PPh4[ReVIICl4(NSCl)2] with excess N(SiMe3)3 in dichloromethane solution to give red‐brown single crystals after recrystallisation from acetonitrile/THF solutions. As a by‐product PPh4[ReNCl4] is formed. (PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] ( 1 ): Space group P21/n, Z = 4, lattice dimensions at –80 °C: a = 1024.1(1), b = 2350.2(1), c = 2315.4(2) pm, β = 94.09(1)°, R1 = 0.0403. In the complex anion of 1 the rhenium atoms are connected by an asymmetric Re≡N–Re bridge as well as by a (NSN)4–‐bridge to form a planar Re2N(NSN) six‐membered heterocycle. Both rhenium atoms are coordinated by three chlorine atoms, one of them by a thionitrosyl ligand, the other one by the oxygen atom of a thf molecule.  相似文献   

14.
Crystal and Molecular Structure of the Solventfree Hexamethyldisilazides of Rubidium and Cesium and the Crystal Structure of a Toluene Solvate X-ray crystal structures are reported for the dimeric rubidium and cesium hexamethyldisilazides [MN(SiMe3)2]2. [RbN(SiMe3)2]2 ( 1 ) crystallizes in the monoclinic space group P21/c with a = 1044.7(2), b = 891.1(2), c = 1281.0(3) pm, β = 100.26(2) °, Z = 2. [CsN(SiMe3)2]2 ( 2 ) crystallizes in the orthorhombic space group Pbca with a = 1270.81(2), b = 1281.16(1), c = 1539.65(2) pm, Z = 4. Both compounds contain a four-membered [M–N–]2-ring located on an inversion centre. The M–N bond lengths are: 287.8(2), 295.6(2) pm ( 1 ) and 307.4(2), 314.9(2) pm ( 2 ). The solvate [CsN(SiMe3)2]2 · C7H8 ( 3 ) crystallizes from toluene in the triclinic space group P1 with a = 854.00(2), b = 979.58(2), c = 1084.45(3) pm, α = 111.482(1), β = 93.821(1), γ = 108.546(1)°, Z = 1. In this compound dimeric units [CsN(SiMe3)2]2 and toluene molecules form a polymeric chain.  相似文献   

15.
Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [AlCl2(NPEt3)]2, [GaI2(NPEt3)]2, and [GaI2(NPPh3)]2 [AlCl2(NPEt3)]2 ( 1 ) is made according to the known method by reaction of aluminium trichloride with the silylated phosphaneimine Me3SiNPEt3 in acetonitrile; it is isolated as colourless, moisture sensitive crystals. The phosphoraneiminato complexes [GaI2(NPEt3)]2 ( 2 ) and [GaI2(NPPh3)]2 ( 3 ), on the other hand, are obtained by redox reactions as pale yellow crystals; ( 2 ) of “gallium(I) iodide” with Me3SiNPEt3 in toluene and ( 3 ) of gallium with N-iodine triphenylphosphaneimine, INPPh3, in tetrahydrofuran. 1 and 3 are characterized spectroscopically and by crystal structure determinations; 2 is characterized only crystallographically. 1 : Space group Pbca, Z = 4; lattice dimensions at –70 °C: a = 1232.6(2), b = 1341.1(2), c = 1393.4(3) pm, R1 = 0.0315. 1 forms centrosymmetric molecules in which the Al atoms are linked via Al–N bonds of the two (NPEt3) groups; with 185.0 and 184.4 pm these bonds are of almost the same lengths. 2 : Space group Pbca, Z = 4; lattice dimensions at –80 °C: a = 1380.0(1), b = 1311.0(1), c = 1429.1(1) pm, R1 = 0.0273. 2 crystallizes isotypically with 1 . The gallium atoms of the centrosymmetric Ga2N2 four-membered ring are connected with Ga–N distances of equal length (190.9 pm). 3 · THF: Space group P212121, Z = 2; lattice dimensions at –140 °C: a = 1494.6(1), b = 1536.3(1), c = 974.6(1) pm, R1 = 0.0382. 3 forms dimeric molecules in which the gallium atoms are linked via the N atoms of the (NPPh3) groups to form a non-planar Ga2N2 four-membered ring of C2 symmetry with Ga–N bonds of equal lengths – within standard deviations – of 194.7 pm. The phosphoraneiminato groups are arranged in a synperiplanar way.  相似文献   

16.
[MoNCl3(THF)]4 – a Nitrido Complex with a Folded Mo4N4 Eight-Membered Ring Red moisture sensitive single crystals of [MoNCl3(THF)]4 ( 1 ) prepared from saturated solutions of CH2Cl2 were characterized by a crystal structure determination. Space group P 4 21c, Z = 2, lattice dimensions at –80 °C: a = b = 1291.2(1), c = 1116.3(1) pm, R = 0.0581. In 1 the molybdenum atoms are linked by nearly linear Mo≡N–Mo bridges with MoN distances of 167 and 216 pm, which corresponds with triple and single bonds. In trans position to the Mo≡N bond the THF molecule is bonded by its oxygen atom. Along the diagonal axis Mo…Mo 1 is folded with an aperture angle of 140° thus forming a butterfly structure.  相似文献   

17.
Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SnI(NPPh3)]2 and [SnI3(NPPh3)]2 The phosphoraneiminato complex of the divalent tin, [SnI(NPPh3)]2 ( 1 ), originates from the reaction of metallic tin with N-iodine triphenylphosphaneimine, INPPh3, in dichloromethane suspension. 1 forms yellow, moisture sensitive crystals, which can be converted into the red phosphoraneiminato complex of the tetravalent tin, [SnI3(NPPh3)]2 ( 2 ), by oxidation with iodine. According to the crystal structure analyses 1 and 2 have centrosymmetric dimeric molecular structures in which the tin atoms are linked via the N atoms of the NPPh3 groups. The tin atoms in 1 have a ψ-tetrahedral coordination, those in 2 a trigonal-bipyramidal one. 1 : Space group P 1, Z = 1, lattice dimensions at –80 °C: a = 779.0(1), b = 1080.1(1), c = 1170.4(1) pm, α = 64.49(1)°, β = 88.42(1)°, γ = 79.13(1)°, R = 0.0293. 2 : Space group P21/n, Z = 2, lattice dimensions at –80 °C: a = 1252.4(1), b = 1421.3(3), c = 1260.1(1) pm, β = 108.50(1)°, R = 0.0518.  相似文献   

18.
Synthesis and Crystal Structure of the Mixed Valent Complex [Sn2I3(NPPh3)3] The mixed valent phosphoraneiminato complex [Sn2I3(NPPh3)3] ( 1 ) was prepared by the reaction of the tin(II) complex [SnI(NPPh3)]2 with sodium in tetrahydrofuran. 1 crystallizes with two formula units of THF to form yellow, moisture sensitive single crystals, which were characterized by a crystal structure determination. 1 · 2 THF: Space group P21/c, Z = 4, lattice dimensions at –80 °C: a = 1964.5(2), b = 1766.0(2), c = 2058.6(2) pm; β = 118.33(1)°, R = 0.052. 1 forms dimeric molecules in which the tin atoms are linked by two nitrogen atoms of two (NPPh3) groups to form a planar Sn2N2 four‐membered ring. The SnIV atom is additionally coordinated by a terminal iodine atom and by a terminal (NPPh3) group, whereas the SnII atom is additionally coordinated by two iodine atoms forming a ψ trigonal‐bipyramidal surrounding.  相似文献   

19.
The Reaction of Ph3AsCl2 with Acetonitrile. Crystal Structures of [Ph3AsNC(Me)C(AsPh3)CN]+Cl and of the Palladium Molecular Complex [Ph3AsNC(Me)C(AsPh3)CN–PdCl3] In the presence of potassium hydride the reaction of Ph3AsCl2 with acetonitrile leads to [Ph3AsNC(Me) · C(AsPh3)CN]+Cl ( 1 ), which is characterized by its infrared spectrum and by a crystal structure analysis. 1 can be explained as an insertion reaction of acetonitrile into an ylidic As–C bond of the primarily formed [(Ph3As)2CCN]Cl. 1 : Space group P1, Z = 2, lattice dimensions at –70 °C: a = 991.9(1), b = 1255.2(1), c = 1381.3(1) pm, α = 81.64(1)°, β = 80.12(1)°, γ = 78.17(1)°; R1 = 0.051. 1 reacts with palladium(II) chloride to give the molecular complex [Ph3AsNC(Me)C(AsPh3)CN–PdCl3] ( 2 ) with zwitterionic structure. The fragment {PdCl3} is terminally bonded at the nitrogen atom of the CCN group of the cation of 1 in a linear arrangement CCNPd. 2 · CH3CN: Space group P21, Z = 2, lattice dimensions at –90 °C: a = 1079.2(1), b = 1261.5(1), c = 1560.9(1) pm; β = 110.20(1)°; R1 = 0.0283.  相似文献   

20.
Amido Metalates of Rare Earth Elements. Syntheses and Crystal Structures of [Na(12-crown-4)2][M{N(SiMe3)2}3(OSiMe3)] (M = Sm, Yb), [Na(THF)3Sm{N(SiMe3)2}3(C≡C–Ph)], [Na(THF)6][Lu2(μ-NH2)(μ-NSiMe3){N(SiMe3)2}4], and of [NaN(SiMe3)2(THF)]2. Applications of Rare Earth Metal Complexes as Polymerization Catalysts The amido silyloxy complexes [Na(12-crown-4)2][M{N(SiMe3)2}3(OSiMe3)] with M = Sm ( 1 a ), Eu ( 1 b ), Yb ( 1 c ), and Lu ( 1 d ) were obtained from the trisamides M[N(SiMe3)3]3 and NaOSiMe3 in n-hexane in the presence of 12-crown-4; they form yellow to orange-red crystals, of which 1 a and 1 c were characterized crystallographically. The complexes crystallize isotypically with one another in the monoclinic space group I2/a with eight formula units per unit cell. The metal atoms of the complex anions are tetrahedrally coordinated by the three nitrogen atoms of the N(SiMe3)2 ligands and by the oxygen atom of the OSiMe3 ligand. With 172.4° for 1 a and 179.3° for 1 c the bond angles M–O–Si are practically linear. With ethynylbenzene in the presence of NaN(SiMe3)2 in tetrahydrofuran the trisamides M[N(SiMe3)2]3 react under formation of the complexes [Na(THF)3M{N(SiMe3)2}3 · (C≡C–Ph)] with M = Ce ( 2 a ), Sm ( 2 b ), and Eu ( 2 c ), of which 2 b was characterized crystallographically (monoclinic, space group P21/n, Z = 4). 2 b forms an ion pair in which the terminal carbon atom of the C≡C–Ph ligand is connected with the samarium atom of the Sm[N(SiMe3)2]3 group and the sodium ion is side-on connected with the acetylido group. According to the crystal structure determination (space group P212121, Z = 4) [Na(THF)6][Lu2(μ-NH2)(μ-NSiMe3) · {N(SiMe3)2}4] ( 3 ), which is formed as a by-product, consists of [Na(THF)6]+ ions and dimeric anions, in which the lutetium atoms are connected to form a planar Lu2N2 four-membered ring via a μ-NH2 bridge with average Lu–N distances of 227.2 pm and via a μ-NSiMe3 bridge of average Lu–N distances of 218.5 pm. According to the crystal structure determination (space group P 1, Z = 1) [NaN(SiMe3)2(THF)]2 ( 4 ) forms centrosymmetric dimeric molecules with Na–N distances of the Na2N2 four-membered ring of 239.9 pm and distances Na–O of the terminally bonded THF molecules which are 226.7 pm. The vinylic polymerization of methylmethacrylate (MMA) catalyzed by 1 c resulted in high molecular weight polymethylmethacrylate (PMMA) with moderate yields. The reaction of 1 a or 2 b with MMA did not give PMMA. Insoluble polynorbornene was obtained in low yields by reaction of norbornene/methylaluminoxane (MAO) with 1 a , 1 c , or 2 b . The ring opening polymerization of ϵ-caprolacton or δ-valerolacton catalyzed by 2 b resulted in corresponding polylactones in quantitative yields.  相似文献   

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