共查询到20条相似文献,搜索用时 15 毫秒
1.
Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N3)4X2]2–, X = Cl, Br, I By oxidative addition to (n‐Bu4N)2[Pt(N3)4] with the elemental halogens in dichloromethane trans‐(n‐Bu4N)2[Pt(N3)4X2], X = Cl, Br, I are formed. X‐ray structure determinations on single crystals of trans‐(Ph4P)2[Pt(N3)4Cl2] (triclinic, space group P1, a = 10.352(1), b = 10.438(2), c = 11.890(2) Å, α = 91.808(12), β = 100.676(12), γ = 113.980(10)°, Z = 1), trans‐(Ph4P)2[Pt(N3)4Br2] (triclinic, space group P1, a = 10.336(1), b = 10.536(1), c = 12.119(2) Å, α = 91.762(12), β = 101.135(12), γ = 112.867(10)°, Z = 1) and trans‐(Ph4P)2[Pt(N3)4I2] (triclinic, space group P1, a = 10.186(2), b = 10.506(2), c = 12.219(2) Å, α = 91.847(16), β = 101.385(14), γ = 111.965(18)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–Cl = 2.324, Pt–Br = 2.472, Pt–I = 2.619 and Pt–N = 2.052–2.122 Å. The approximate linear Azidoligands with Nα–Nβ–Nγ‐angles = 172.1–176.8° are bonded with Pt–Nα–Nβ‐angles = 116.2–121.9°. In the vibrational spectra the platinum halogen stretching vibrations of trans‐(n‐Bu4N)2[Pt(N3)4X2] are observed in the range of 327–337 (X = Cl), at 202 (Br) and in the range of 145–165 cm–1 (I), respectively. The platinum azide stretching modes of the three complex salts are in the range of 401–421 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtCl) = 1.90, fd(PtBr) = 1.64, fd(PtI) = 1.22, fd(PtNα) = 2.20–2.27 and fd(NαNβ, NβNγ) = 12.44 mdyn/Å. 相似文献
2.
Synthesis and Spectroscopic Characterization of Fluorocarbonylosmates, Normal Coordinate Analysis and Crystal Structure of fac -[OsF3Br2(CO)]2– By treatment of (n-Bu4N)2[OsBr5(CO)] with TlF in C6H5CF3 fac-(n-Bu4N)2[OsF3Br2(CO)] is formed, from which salts with the cations (Et4N)+, (py2CH2)2+, Tl+ and Cs+ are obtainable. Oxidation of the by-product [OsF5(CO)]2– with Cl2 yields [OsF5(CO)]– which 19F NMR spectrum reveals a quintet (δF = 89.9) and a dublet (43.5 ppm) in the ratio 1 : 4 with coupling constants 2JFF = 94.9 Hz. Simultaneously produced mer-[OsF3Cl2(CO)]– exhibits in the high field region a triplet (δF = –70.4) and a dublet (–66.2 ppm) in the ratio 1 : 2 and 2JFF = 9.5 Hz. The X-ray structure determinations of fac-Tl2[OsF3Br2(CO)] ( 1 ) (monoclinic P21/n, a = 11.143(12), b = 11.654(4), c = 13.751(10) Å, β = 91.50(6)°, Z = 8) and fac-(py2CH2)[OsF3Br2(CO)] · 1/2(CH3)2CO ( 2 ) (triclinic, P 1, a = 8.432(1), b = 9.009(1), c = 12.402(2) Å, α = 80.30(1), β = 79.68(2), γ = 68.14(1)°, Z = 2) result in nearly Cs symmetry of the complex anion with bond lengths in the ranges Os–F = 1.98–2.08, Os–Br = 2.45–2.46, Os–C = 1.83–1.84, C–O = 1.10 – 1.17 Å. Using the molecular parameters of the X-ray determinations the IR spectra have been assigned by normal coordinate analysis. The valence force constants are fd(CO) = 15.4–15.7, fd(OsC) = 4.4–4.7, fd(OsF) = 2.4–2.7, fd(OsF˙) = 1.6–2.0, fd(OsBr) = 1.7–2.1 mdyn/Å. 相似文献
3.
Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans ‐( n ‐Bu4N)4[Pt(ECN)2(ox)2], E = S, Se By reaction of (n‐Bu4N)2[Pt(ox)2] with (SCN)2 and (SeCN)2 in dichloromethane trans‐(n‐Bu4N)2[Pt(SCN)2(ox)2] ( 1 ) und trans‐(n‐Bu4N)2[Pt(SeCN)2(ox)2] ( 2 ) are formed. The crystal structures of 1 (triclinic, space group P1, a = 10.219(2), b = 11.329(2), c = 12.010(3) Å, α = 114.108(15), β = 104.797(20), γ = 102.232(20)°, Z = 1) and 2 (triclinic, space group P1, a = 10.288(1), b = 11.332(1), c = 12.048(1) Å, α = 114.391(9), β = 103.071(10), γ = 102.466(12)°, Z = 1) reveal, that the compounds crystallize isotypically with centrosymmetric complex anions. The bond lengths are Pt–S = 2.357, Pt–Se = 2.480 and Pt–O = 2.011 ( 1 ) und 2.006 Å ( 2 ). The oxalato ligands are nearly plane with O–C–C–O torsion angles of 1.7–3.6°. The via S or Se coordinated linear groups are inclined between both oxalato ligands with Pt–E–C angles of 100.4 (E = S) and 97.4° (Se). In the vibrational spectra the PtE stretching vibrations are observed at 299–314 ( 1 ) and 189–200 cm–1 ( 2 ). The PtO stretching vibrations are coupled with internal vibrations of the oxalato ligands and appear in the range of 400–800 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtS) = 1.75, fd(PtSe) = 1.35 and fd(PtO) = 2.77 mdyn/Å. The NMR shifts are δ(195Pt) = 5435.2 ( 1 ), 5373.7 ( 2 ) and δ(77Se) = 353.2 ppm with the coupling constant 1J(SePt) = 37.4 Hz. 相似文献
4.
The blue tetranuclear CuII complexes {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O ( 1 ) and {[Cu(phen)(OH)]4(H2O)2}Cl4 · 4 H2O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) Å3, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) Å3, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]4Cl2}2+ and {[Cu(phen)(OH)]4(H2O)2}4+ complex cations formed by condensation of four elongated square pyramids CuN2(OH)2Lap with the apical ligands Lap = Cl, H2O, OH. The resulting [Cu4(μ2‐OH)2(μ3‐OH)2] core has the shape of a zigzag band of three Cu2(OH)2 squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl– anions and H2O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Clap = 2.563; Cu–Oap(OH) = 2.334–2.369 Å; Cu–Oap(H2O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χm(T‐θ) = 0.933 cm3 · mol–1 · K with θ = –0.7 K). 相似文献
5.
Preparation and Properties of Tetra(n-butyl)ammonium cis -Trifluorophthalocyaninato(2–)zirconate(IV) and -hafnate(IV); Crystal Structure of (nBu4N) cis [Hf(F)3pc2–] cis-Dichlorophthalocyaninato(2–)metal(IV) of zirconium and hafnium reacts with excess tetra(n-butyl)-ammoniumfluoride trihydrate to yield tetra(n-butyl)-ammonium cis-trifluorophthalocyaninato(2–)metalate(IV), (nBu4N)cis[M(F)3pc2–] (M = Zr, Hf). (nBu4N)cis[Hf(F)3pc2–] crystallizes in the monoclinic space group P21/n (# 14) with cell parameters a = 13.517(1) Å, b = 13.856(1) Å, c = 23.384(2) Å, α = 92.67(1)°, Z = 4. The Hf atom is in a ”︁square base-trigonal cap”︁”︁ polyhedron, coordinating three fluorine atoms and four isoindole nitrogen atoms (Niso). The Hf atom is sandwiched between the (Niso)4 and F3 planes (d(Hf–CtN) = 1.218(3) Å; d(Hf–CtF) = 1.229(3) Å; CtN/F: centre of the (Niso)4, respectively F3 plane). The average Hf–Niso and Hf–F distances are 2.298 and 1.964 Å, respectively, the average F–Hf–F angle is 84.9°. The pc2– ligand is concavely distorted. The optical spectra show the typical metal independent π-π* transitions of the pc2– ligand at c. 14700 and 29000 cm–1. In the FIR/MIR spectra vibrations of the MF3 skeleton are detected at 545, 489, 274 cm–1 (M = Zr) and 536, 484, 263 cm–1 (M = Hf), respectively. 相似文献
6.
trans -Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II): Synthesis, Properties, and Crystal Structure Dirheniumheptoxide reacts with phthalodinitrile in boiling 1-chloronaphthalene and subsequent reprecipitation of the green raw product from conc. sulfuric acid to yield an oxo-phthalocyaninate of rhenium, which is reduced by molten triphenylphosphine forming dark green trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), trans[Re(PPh3)2pc2–]. The latter crystallizes triclinic in the space group P 1 with the cell parameters as follows: a = 11.512(2) Å, b = 12.795(2) Å, c = 12.858(2) Å, α = 64.42(2)°, β = 79.45(2)°, γ = 72.74(1)°; V = 1628.1(5); Z = 1. Re is in the centre of the (Np)4 plane (Np: N1, N3) and coordinates two triphenylphosphine ligands axially in trans position. The average Re–Np and Re–P distances are 2.007(1) and 2.516(3) Å, respectively. Despite the many extra bands the typical B, Q and N regions of the pc2– ligand are observed at ca. 16500, 28900/32900 and 35300 cm–1. A weak band group at ca. 8900 cm–1 is attributed to a trip-multiplet transition, another one at ca. 14500 cm–1 to a P → Re charge transfer. The vibrational spectra are dominated by internal vibrations of the pc2– ligand. The very weak intensity of the IR bands at 905 and 1327 cm–1 are diagnostic of the presence of ReII. 相似文献
7.
Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), cis[Tl(X)2pc2–]– (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (nBu4N)X in dichloromethane, and isolated as (nBu4N)cis[Tl(X)2pc2–]. (nBu4N)cis[Tl(ONO′)2pc2–] ( 1 ) and (nBu4N)cis[Tl(X)2pc2–] · 0,5 (C2H5)2O ( 2 ) crystallize in the monoclinic space group P21/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (Niso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–Niso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four Niso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–Niso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (Niso)4 plane (CtN) towards the acido ligands (d(Tl–CtN) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed. 相似文献
8.
Synthesis,Crystal Structure and Selected Properties of Mono(dithiocarbamato)‐gold(I), AuS2CNH2
下载免费PDF全文
![点击此处可从《无机化学与普通化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Christoph Ludwig Teske Helge Reinsch Huayna Terraschke Wolfgang Bensch 《无机化学与普通化学杂志》2017,643(7):466-470
The title compound AuS2CNH2 was prepared from an aqueous solution by reaction of dicyanidoaurate [Au(CN)2]– with excess of ammoniumdithiocarbamate NH4S2CN H 2 at pH ≈ 2. The compound crystallizes in the orthorhombic space group Cmma with a = 6.4597(2), b = 12.6556(3), and c = 5.3235(1) Å. The crystal structure comprises linear S–Au–S dumbbells forming unbranched zigzag chains in combination with the dithiocarbamate ligands. The three‐dimensional arrangement of the molecules is realized by aurophilic AuI–AuI and hydrogen bonding interactions, respectively. AuS2CNH2 presents orange luminescence due to a broad emission band between 12000 cm–1 and 23000 cm–1 (ν = 26316 cm–1). 相似文献
9.
Treatment of copper(I) chloride with R2Si(NLiPh)2 (R = Me, Ph) in thf led to the formation of the octanuclear cluster compounds [Cu8{(R2Si(NPh)2}4] [R = Me ( 1 ), Ph ( 2 ).] Compound 1 crystallizes in the tetragonal space group P4/n, with a = 1505.41(5) and c = 1911.32(7) pm. The X‐ray crystal structure determination revealed a cube shaped Cu8 cluster core with μ4 bridging Me2Si(NPh)22– ligands. The copper atoms display an almost linear coordination with Cu–N distances in the range of 191.1(3)–191.4(3) pm. The Cu–Cu distances are 265.7(1)–267.3(1) pm. Compound 2 forms monoclinic crystals, space group P21/n, with a = 1461.87(4), b = 2483.77(6), c = 2725.49(8) pm, β = 100.77(1)°. The cluster core of compound 2 consists formally of two mutually perpendicular arranged trigonal prisms, which share a common square face. Like in the case of compound 1 the square faces of the cluster core are capped by μ4 bridging Ph2Si(NPh)22– ligands. The copper atoms adopt a nearly linear N–Cu–N coordination with Cu–N distances of 190.0(4)–195.1(4) pm. The Cu–Cu distances are 252.3(1)–305.6(1) pm. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(2):266-276
N-(R-carbamothioyl)cyclohexanecarboxamides (R: diethyl, di-n-propyl, di-n-butyl, diphenyl and morpholine-4) and their Ni(II) and Cu(II) complexes have been synthesized and characterized by elemental analyses, FT-IR and NMR methods. N-(diethylcarbamothioyl)cyclohexanecarboxamide, HL1, C12H22N2OS, crystallizes in the orthorhombic space group P212121, with Z = 4, and unit cell parameters, a = 6.6925(13) Å, b = 9.0457(18) Å, c = 22.728(5) Å. The conformation of the HL1 molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as reflected by the torsion angles O1–C6–N2–C5, C6–N2–C5–N1 and S1–C5–N2–C6 of 1.68°, ?67.47° and 115.50°, respectively. The structure of HL1 also shows a delocalization of the π electrons of the thiocarbonyl group over the C–N bonds. The ring puckering analysis shows that the cyclohexane ring has a chair conformation. The bis(N-(morpholine-4-carbonothioyl)cyclohexane carboxamido)nickel(II) complex, Ni(L5)2, C24H38N4NiO4S2, crystallizes in the monoclinic space group P21/c, with Z = 4, and unit cell parameters, a = 16.919(3) Å, b = 8.3659(17) Å, c = 19.654(4) Å, β = 107.43(3)°. Ni(L5)2 is a cis-complex with a slightly distorted square-planar coordination of the central nickel by two oxygen and two sulfur atoms. 相似文献
11.
Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N3)6]2– and [Pt(N3)Cl5]2–, 195Pt and 15N NMR Spectra of [Pt(N3)nCl6–n]2– and [Pt(15NN2)n(N215N)6–n]2–, n = 0–6 By ligand exchange of [PtCl6]2– with sodium azide mixed complexes of the series [Pt(N3)nCl6–n]2– and with 15N‐labelled sodium azide (Na15NN2) mixtures of the isotopomeres [Pt(15NN2)n(N215N)6–n]2–, n = 0–6 and the pair [Pt(15NN2)Cl5]2–/[Pt(N215N)Cl5]2– are formed. X‐ray structure determinations on single crystals of (Ph4P)2[Pt(N3)6] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph4As)2[Pt(N3)Cl5] · HCON(CH3)2 ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with Nα–Nβ–Nγ‐angles = 173.5–174.6° are bonded with Pt–Nα–Nβ‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu4N)2[Pt(N3)Cl5] are observed at 318–345, the PtN stretching modes of (n‐Bu4N)2[Pt(N3)6] at 401–428 and of (n‐Bu4N)2[Pt(N3)Cl5] at 408–413 cm–1. The mixtures (n‐Bu4N)2[Pt(15NN2)n(N215N)6–n], n = 0–6 and (n‐Bu4N)2[Pt(15NN2)Cl5]/(n‐Bu4N)2[Pt(N215N)Cl5] exhibit 15N‐isotopic shifts up to 20 cm–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are fd(PtCl) = 1.93, fd(PtNα) = 2.38 and fd(NαNβ, NβNγ) = 12.39 mdyn/Å. In the 195Pt NMR spectrum of [Pt(N3)nCl6–n]2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The 15N NMR spectrum of (n‐Bu4N)2[Pt(15NN2)n(N215N)6–n], n = 0–6 exhibits by 15N–195Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal 15N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm. 相似文献
12.
An ampule reaction between Mo and PCl5 at 200 °C yielded (PCl4)2[Mo2Cl10], the first ternary compound in Mo–P–Cl system. Single crystal X-ray diffraction gave a triclinic unit cell: a = 6.870(1), b = 8.892(2), c = 9.423(2) Å, α = 100.24(2), β = 95.55(2), γ = 96.12(2)° (V = 559.3(2) Å3, Z = 1, sp. gr. P1, wR2 = 0.0575 and R1 = 0.0279. The ionic compound is built from edge sharing bioctahedra [Mo2Cl10]2– and two tetrahedra PCl4+. The averaged Mo–Clb distance, 2.503(1) Å, is longer than the Mo–Clt distance, 2.33(2) Å. The Mo … Mo distance, 3.77 Å, indicates the absence of a direct Mo–Mo interaction. Semiempirical and ab initio calculations showed the possibility for [Mo2Cl10]2– to exist with long and short Mo to Mo distances, the letter corresponding to the Mo–Mo bond. 相似文献
13.
Weak Sn…I Interactions in the Crystal Structures of the Iodostannates [SnI4]2– and [SnI3]– Iodostannate complexes can be crystallized from SnI2 solutions in polar organic solvents by precipitation with large counterions. Thereby isolated anions as well as one, two or three‐dimensional polymeric anionic substructures are established, in which SnI3– and SnI42– groups are linked by weak Sn…I interactions. Examples are the iodostannates [Me3N–(CH2)2–NMe3][SnI4] ( 1 ), (Ph4P)2[Sn2I6] ( 2 ), [Me3N–(CH2)2–NMe3][Sn2I6] ( 3 ), [Fe(dmf)6][SnI3]2 ( 4 ) and (Pr4N)[SnI3] ( 5 ), which have been characterized by single crystal X‐ray diffraction. [Me3N–(CH2)2–NMe3][SnI4] ( 1 ): a = 671.6(2), b = 1373.3(4), c = 2046.6(9) pm, V = 1887.7(11) · 106 pm3, space group Pbcm;(Ph4P)2[Sn2I6] ( 2 ): a = 1168.05(6), b = 717.06(4), c = 3093.40(10) pm, β = 101.202(4)°, V = 2541.6(2) · 106 pm3, space group P21/n;[Me3N–(CH2)2–NMe3][Sn2I6] ( 3 ): a = 695.58(4), b = 1748.30(8), c = 987.12(5) pm, β = 92.789(6)°, V = 1199.00(11) · 106 pm3, space group P21/c;[Fe(dmf)6][SnI3]2 ( 4 ): a = 884.99(8), b = 1019.04(8), c = 1218.20(8) pm, α = 92.715(7), β = 105.826(7), γ = 98.241(7), V = 1041.7(1) · 106 pm3, space group P1;(Pr4N)[SnI3] ( 5 ): a = 912.6(2), b = 1205.1(2), c = 1885.4(3) pm, V = 2073.5(7) · 106 pm3, space group P212121. 相似文献
14.
Ammonium and guanidinium difluoroiodate(V), [NH4]+[IF2O2]– ( 1a ) and [C(NH2)3]+[IF2O2]– ( 1b ), and diazidoglyoxime, [N3C=N–OH]2 ( 2 ) were synthesized and the molecular structures in the solid state of 1b and 2 were elucidated by single‐crystal X‐ray diffraction. 1b : P$\bar{1}$ , a = 6.6890(5), b = 10.2880(6), c = 10.30.92(8) Å, α = 105.447(6), β = 108.568(7), γ = 91.051(5)°, V = 644.08(8) Å3, ρ = 2.650 g · cm–3; 2 : P21/n, a = 4.4211(3), b = 13.7797(9), c = 4.9750(3) Å, β = 98.735(6), V = 299.57(3) Å3, ρ = 1.886 g · cm–3. The suitability of compounds 1a and 1b as active ingredients for agent defeat weapons (ADW) with biocidal activity has been shown in detonation tests using geobacillus stearothermophilus spores. In addition, a complete energetic characterization of the promising primary explosive 2 is given. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(9):1468-1475
Reactions of copper(I) halides (X = Cl, Br, I) with thiophene-2-carbaldehyde thiosemicarbazone and triphenylphosphine in 1 : 1 : 2 molar ratio yield tetrahedral mononuclear complexes, [CuX(η1-S-Httsc)(Ph3P)2] (X = Cl, 1; Br, 2; I, 3), characterized by elemental analysis, IR, NMR (1H, 13C, 31P), and single crystal X-ray crystallography (1). The unit cell of 1 has two independent distorted tetrahedral molecules (1a and 1b) with different bond parameters. One acetonitrile is entrapped between them. Crystal data: C86H77Cl2Cu2N7P4S4 1: triclinic, P-1, a = 12.8810(9), b = 18.5049(13), c = 18.7430(13) Å, α = 63.7130(10), β = 89.0960(10), γ = 85.5010(10)°, V = 3992.4(5) Å3, Z = 2, R (int) = 0.0314. Bond parameters: 1a, Cu(1A)–Cl(1A), 2.3803(5); Cu(1A)–S(1A), 2.3822(5); Cu(1A)–P(1A), 2.2498(5) Å; P(1A)–Cu(1A)–P(2A), 124.294(19)°; 1b, Cu(1B)–Cl(1B), 2.3975(5); Cu(1B)–S(1B), 2.3756(5); Cu(1B)–P(1B), 2.2777(5) Å; P(1B)–Cu(1B)–P(2B), 127.156(19)°. 相似文献
16.
G. Fritz E. Matern H. Krautscheid R. Ahlrichs J. W. Olkowska J. Pikies 《无机化学与普通化学杂志》1999,625(10):1604-1607
Formation and Structure of the iso -Tetraphosphane P(PtBu2)3: a Molecule with a Planar Three-coordinated P Atom The iso-tetraphosphane P(PtBu2)3 ( 1 ) was obtained by irradiating tBu2P–P=P(Me)tBu2 ( 3 ). 1 forms hexagonal crystals (space group P63/m) with a = 1005,63(8), c = 1621,4(2) pm, Z = 2. The P(PtBu2)3 molecules are arranged in a hexagonally close packed lattice. The four P atoms in each molecule are coplanar with P–P bond distances 219.08(4) pm and P–P–P angles 120°. The observed planar geometry is in accordance with ab initio calculations. 相似文献
17.
Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N3)4(ECN)2]2–, E = S, Se By oxidative addition to (n‐Bu4N)2[Pt(N3)4] with dirhodane in dichloromethane trans‐(n‐Bu4N)2[Pt(N3)4(SCN)2] and by ligand exchange of trans(n‐Bu4N)2[Pt(N3)4I2] with Pb(SeCN)2 trans‐(n‐Bu4N)2[Pt(N3)4(SeCN)2] are formed. X‐ray structure determinations on single crystals of trans‐(Ph4P)2[Pt(N3)4(SCN)2] (triclinic, space group P 1, a = 10.309(3), b = 11.228(2), c = 11.967(2) Å, α = 87.267(13), β = 75.809(16), γ = 65.312(17)°, Z = 1) and trans‐(Ph4P)2[Pt(N3)4(SeCN)2] (triclinic, space group P 1, a = 9.1620(10), b = 10.8520(10), c = 12.455(2) Å, α = 90.817(10), β = 102.172(10), γ = 92.994(9)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–S = 2.337, Pt–Se = 2.490 and Pt–N = 2.083 (S), 2.053 Å (Se). The approximate linear Azidoligands with Nα–Nβ–Nγ‐angles = 172,1–175,0° are bonded with Pt–Nα–Nβ‐angles = 116,7–120,5°. In the vibrational spectra the platinum chalcogen stretching vibrations of trans‐(n‐Bu4N)2[Pt(N3)4(ECN)2] are observed at 296 (E = S) and in the range of 186–203 cm–1 (Se). The platinum azide stretching modes of the complex salts are in the range of 402–425 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtS) = 1.64, fd(PtSe) = 1.36, fd(PtNα) = 2.33 (S), 2.40 (Se) and fd(NαNβ, NβNγ) = 12.43 (S), 12.40 mdyn/Å (Se). 相似文献
18.
Jens Mahnke Andreas Zanin Wolf-Walther du
Mont Frank Ruthe Peter G. Jones 《无机化学与普通化学杂志》1998,624(9):1447-1454
The New P -Phosphanylphosphaalkene 1-Bis(trimethylsilyl)methylidene-2,2-diisopropyldiphosphane: First Reactions at its P=C and P–P Bonds (Me3Si)2C=PCl ( 1 ) reacts with the trichlorosilylphosphanes RR′PSiCl3 (R and R′ = t-Bu or i-Pr) providing the new P-dialkylphosphanylphosphaalkenes (Me3Si)2C=P–P-i-Pr2 ( 2 ) and (Me3Si)2C=P–P(t-Bu)(i-Pr) ( 3 ) as well as the known (Me3Si)2C=P–P-t-Bu2 ( 4 ). The P=C double bond of 2 can be protected reversibly by a [2 + 4]-cycloaddition with cyclopentadiene resulting in the formation of a P-phosphanyl-phosphanorbornene derivative 5 . The [2 + 4]-cycloaddition of 2 with 2,3-dimethylbutadiene provides the cyclic diphosphane 6 . Reactions of 2 with sulfur and selenium were followed by 31P and 77Se nmr: Chalcogen insertion into the P–P bond leads to the products (Me3Si)2C=P–X–P-i-Pr2 9 a (X = S) and 9 b (X = Se). Subsequent σ3λ3 → σ4λ5 oxidation steps of 9 a with S and of 9 b with Se lead to compounds (Me3Si)2C=P–X–P(=X)-i-Pr2 10 a (X = S) and 10 b (X = Se), which contain phosphinic acid functions with the phosphaalkene moieties attached to S or Se. 10 a and 10 b were not isolated in a pure state. However, trapping 10 b from an enriched solution by [2 + 4]-cycloaddition with cyclopentadiene allowed the isolation of the P-diseleno-phosphinato-phosphanorbornene 12 . The constitution of new compounds 2 , 3 , 5 , 6 and 12 was confirmed by elemental analyses, nmr and mass spectra. The structures of cycloadducts 5 and 6 were determined by X-ray diffraction analysis. 相似文献
19.
Colorless platelets of Na2Lu3I3[TeO3]4 were obtained within five days at 775 °C by the reaction of Lu2O3 and TeO2 in a 3:8 molar ratio with NaI added in excess as both fluxing agent and reactant in evacuated silica ampoules. It crystallizes in the monoclinic space group P2/c with the lattice parameters a = 921.69(5), b = 552.71(3), c = 1664.37(9) pm, β = 90.218(4)° and Z = 2. The crystal structure of Na2Lu3I3[TeO3]4 exhibits two crystallographically different Lu3+ cations, both coordinated by eight O2– anions as square antiprisms. These polyhedra are interconnected through four common edges to build up {}^2_∞ {[LuO{}^e_8/2 ]5–} layers (e = edge‐linking) parallel to (100). Furthermore, the crystal structure includes a crystallographically unique Na+ cation surrounded by four O2– and four I– anions also in the shape of a square antiprism. These polyhedra connect via common (I2)–···(I2)– edges in generating {}^1_∞ {[Na2O8I{}^e_4 ]18–} double‐strands that are further linked by (I1)– vertices to result in the formation of {}^2_∞ {[Na2O8I3{}^e,v_3 ]17–} layers (v = vertex‐linking) spreading out parallel to (100) as well. Thus, the crystal structure contains two crystallographically distinct I– anions, of which (I1)– is coordinated nearly linear (? (Na–I1–Na) = 179.6°) by two Na+ cations, whereas (I2)– has contact to three of them displaying a distance of 114 pm from the triangular (Na+)3 plane. The crystal structure of Na2Lu3I3[TeO3]4 is completed by two crystallographically independent Te4+ cations that show stereochemically active non‐bonding electron pairs (“lone pairs”) and are located above and below the {}^2_∞ {[LuO{}^e_8/2 ]5–} layers forming isolated ψ1‐tetrahedral [TeO3]2– anions (d(Te–O) = 188–190 pm) with all oxygen atoms. 相似文献
20.
Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Chloro-Iodo-Rhenates(IV) (CH2Py2)[ReCl5I], cis -(CH2Py2)[ReCl4I2] · 2 DMSO, trans -(CH2Py2)[ReCl4I2] · 2 DMSO, and fac -(EtPh3P)2[ReCl3I3] [ReCl5I]2–, cis-[ReCl4I2]2–, trans-[ReCl4I2]2–, and fac-[ReCl3I3]2– have been synthesized by ligand exchange reactions of [ReI6]2– with HCl and are separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations have been performed on single crystals of (CH2Py2)[ReCl5I] ( 1 ) (triclinic, space group P1 with a = 7.685(2), b = 9.253(2), c = 12.090(4) Å, α = 90.06(2), β = 101.11(2), γ = 95.07(2)°, Z = 2), cis-(CH2Py2)[ReCl4I2] · 2 DMSO ( 2 ) (triclinic, space group P1 with a = 8.662(2), b = 12.109(2), c = 12.9510(12) Å, a = 97.533(11), β = 96.82(2), γ = 89.90(2)°, Z = 2) , trans-(CH2Py2)[ReCl4I2] · 2 DMSO ( 3 ) (triclinic, space group P1 with a = 9.315(7), b = 9.663(3), c = 15.232(3) Å, α = 80.09(2), β = 81.79(4), γ = 83.99(5)°, Z = 2) and fac-(EtPh3P)2[ReCl3I3] ( 4 ) (monoclinic, space group P21/a with a = 17.453(2), b = 13.366(1), c = 19.420(1) Å, β = 112.132(8)°, Z = 4). The crystal structure of ( 1 ) reveals a positional disorder of the anion sublattice along the asymmetric axis. Due to the stronger trans influence of I compared with Cl on asymmetric axes Cl˙–Re–I′ is caused a mean lenghthening of the Re–Cl˙ distances of 0.020 Å (0.8%) and a shortening of the Re–I′ distances of 0.035 Å (1.3%) with regard to symmetrically coordinated axes Cl–Re–Cl and I–Re–I, respectively. Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts of all four chloro-iodo-rhenates(IV) are assigned by normal coordinate analyses. The weakening of the Re–Cl˙ bonds and the strengthening of the Re–I′ bonds is indicated by a decrease or increase of the valence force constants each by 9%. 相似文献