Heterometall-Komplexe mit E6-Liganden (E = P,As)

Heterometallic Complexes with E₆ Ligands (E = P, As) The reaction of [Cp*Co(μ-CO)]₂ 1 with the sandwich complexes [Cp*Fe(η⁵-E₅)] 2 a: E = P, 2 b: E = As in decalin at 190°C affords besides [CpCo₂E₄] 4: E = P, 7: E = As and [CpFe₂P₄] 5 the trinuclear complexes [(Cp*Fe)₂(Cp*Co)(μ-η²-P₂)(μ₃-η^1:2:1-P₂)₂] 3 as well as [(Cp*Fe)₂(Cp*Co)(μ₃-η^2:2:2-As₃)₂] 6 . With [Mo(CO)₅(thf)] 3 and 6 form in a build-up reaction the tetranuclear clusters [(Cp*Fe)₂(Cp*Co)E₆{Mo(CO)₃}] 10: E = P, 11: E = As. 3, 6 and 11 have been further characterized by an X-ray crystal structure determination.     

Synthese und Strukturbestimmung von (i-Pr)2NB(t-BuP)3 und (i-Pr)2NB(t-BuP)4

Synthesis and Structure Analysis of (i-Pr)₂NB(t-BuP)₃ and (i-Pr)₂NB(t-BuP)₄ The diphosphide K(t-Bu)P-(t-BuP)₂-P(t-Bu)K obtained by the cleavage reaction of the 3-membered ring system (i-Pr)₂BN(t-BuP)₂ with potassium reacts with t-BuPCl₂ at ?78°C under ring expansion to form the P₃B ring system (i-Pr)₂NB(t-BuP)₃ – 1,2,3-tri-t-butyl-tri-phospha-4-diisopropyl-aminoboretane ( 1 ). – The 5-membered P₄B ring system (i-Pr)₂NB(t-BuP)₄ – 1,2,3,4-tetra-t-butyl-tetraphospha-5-diisopropylaminoborolidine, ( 2 ) – is formed from K(t-Bu)P? (t-BuP)₂? P(t-Bu)K and (i-Pr)₂NBCl₂ analogous to the above reaction. 1 and 2 could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analysis. 1 shows at 200 K two conformation isomers; for 2 ³¹P-^10,11B-isotopic shifts could be identified.     

Synthese und Kristallstrukturen von (PPh4)2[As2Se4Cl12] und (PPh4)2[As2Se4Br12]

Synthesis and Crystal Structures of (PPh₄)₂[As₂Se₄Cl₁₂] and (PPh₄)₂[As₂Se₄Br₁₂] The reaction of PPh₄Cl and As₂Se₃ with SOCl₂ or with chlorine in dichloromethane affords (PPh₄)₂[As₂Se₄Cl₁₂] with good yields. From PPh₄Br, As₂Se₃ and bromine the corresponding bromo compound was obtained. According to the X-ray crystal structure determinations both compounds are isotypic, crystallizing in the space group of P1 . In the anions two Se₂X₂ molecules are linked with two X^? ions forming an Se₄X₂ ring in chair conformation. Each X^?-ion is associated with an additional AsX₃ molecule (X = Cl, Br).     

Synthesis,halogenation and structural characterization of (Z)-1-[2-(triphenylstannyl)vinyl]-l-cyclododecanol

Synthesis and characterization of (Z)-1-[2-(triphenylstannyl)vinylj-l-cyclododecanol,c-(CH2)11C(OH)CH=CHSnPh3,are reported,together with its halogenation by I2,Br2 and IC1 to yield derivatives of the types c-(CH2)11C(OH)CH=CHSnPh3_nXn (n=1,2; X=I,Br,Cl,respectively).The molecular structures of two compounds have been determined by X-ray diffraction analysis.The tin atom exhibits a distorted tetrahedral geometry in the crystal of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cyclododecanol,but a trigonal bipyramidal geometry in the monoiodo-derivative (Z)-1-[2-(diphenyliodo-stannyl)vinyl]-l-cyclododecanol and other derivatives,in which significant intramolecular coordinative interaction HO→Sn is observed.And the formation of a five-membered tin containing ring is significant for their antitumour activities.     

Synthesis and Crystal Structure of [Sm（4-Pyta）3（H2O）2]n （4-Pyta = 4-Pyridylthioacetate）

A novel coordination polymer [Sm（4-Pyta）3（H2O）2]n has been synthesized by the hydrothermal reaction between 4-Pyta （4-Pyta = 4-pyridylthioacetate） and Sm（NO3）3. The structure was characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space groupP1, with a = 9.100（2）, b = 11.842（3）, c = 12.183（3） A, α= 79.781（4）, β= 74.124（4）, γ = 841882（5）^o, V = 1241.6（5） A^3, Z = 2, Mr = 690.95, Dc = 1.84806 g/cm^3, F（000） = 686,μ = 2.669 mm^-1, the final R = 0.0388 and wR = 0.0808 for 4149 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex exhibits a one-dimensional architecture. Intermolecular hydrogen bonding interactions are found in the complex molecules.     

Synthesis,halogenation and structural characterization of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cyclododecanol

Synthesis and characterisation of (Z)-1-[2(triphenylstannyl)vinyl]-l-cyclododecanol, c-(CH₂)₁₁C(OH)CH=CHSnPh₃, are reported, together with its halogenation by I₂, Br₂ and ICI to yield derivatives of the types c-(CH₂)₁₁C(OH)CH=CHSnPhs_?nX_n (n=1, 2; X=I, Br, Cl, respectively). The molecular structures of two compounds have been determined by X-ray diffraction analysis. The tin atom exhibits a distorted tetrahedral geometry in the crystal of (Z)-l-[2–(triphenylstannyI)vinyl]-l-cyclododecanol, but a trigonal bipyramidal geometry in the monoiodo-derivative (Z)-l-[2]-(diphenyliodo-stannyl)vinyl)-1-cyclododecanol and other derivatives, in which significant intramolecular coordinative interaction HO→Sn ia observed. And the formation of a five-membered tin containing ring is significant for their antitumour activities.     

Monomere Komplexe NiL mit vierzähnigen Liganden [R2P(S)N–R'–NP(S)R2]2– (= L) [1]

Monomeric Complexes NiL with Tetradentate Ligands [R₂P(S)N–R'–NP(S)R₂]^2– (= L) Metathesis of [NiCl₂(PPh₃)₂] with Li salts of the potentially tetradentate ligands [R₂P(S)N–R'–NP(S)R₂]^2– (= L) affords monomeric complexes NiL containing the chromophore NiN₂S₂ ( 1 : R = Et; a , b : R' = Me₂C–(CH₂)₂–CMe₂, o-Phenylen; 2 : R = t-Bu, R' = (CH₂)_n; a – c : n = 2, 3, 4). According to the results of magnetic measurements and VIS as well as NMR spectroscopy (¹H, ³¹P) these complexes are planar except 1 a that is tetrahedral. In case of 1 a and 2 c this was confirmed by the results of crystal structure analyses. In toluene, however, 1 a and 2 c form an equilibrium of planar (diamagnetic) and tetrahedral (paramagnetic) conformers. VT-¹H-NMR including ¹H,¹H-COSY showed a hindered Δ,Λ-inversion of 1 a below 330 K. Only with 1 b a pentacoordinate adduct 1 b · PPh₃ was obtained that completely dissociates in its components on dissolving in benzene. 1 a and 2 c crystallize in the monoclinic space group P2₁/c containing 4 molecules in the unit cell of the dimensions 1 a : a = 8.774(1), b = 12.335(2), c = 21.339(3) Å, β = 92.33(1)° and 2 c : a = 13.374(8), b = 16.197(8), c = 12.814(6) Å, β = 109.20(4)°. The coordination of the Ni atom yields in 1 a a dihedral angle ϵ of 41.7(1)° and thus a geometry intermediate between planar and tetrahedral while in 2 c the angle of 4.5(1)° reveals a nearly planar chromophore NiN₂S₂.     

Synthesis of trans,trans-[MoX2py4][MoX4py2], trans-[MoX2py4]Br3, and structural identification of trans,trans-[MoX2py4][MoX4py2] (X = Cl,Br; py = pyridine)

Trans,trans-[MoX₂py₄][MoX₄py₂] (X = Cl, A; Br, B; py = pyridine, C₅H₅N) are the side products of reaction of between (NH₄)₂[MoX₅ · H₂O] (X = Cl,Br) with pyridine diluted with methanol. Both trans,trans-[MoX₂py₄][MoX₄py₂] are monoclinic, P2₁/n space group, with z = 2 and: a = 12.568(1), b = 9.430(1), c = 14.952(1) Å and β = 100.81(1)° (A); a = 12.551(2), b = 9.533(2), c = 15.366(2) (Å) and β = 99.35(1) (B). Cations and anions are located on the symmetry centers and have eclipsed conformation of the trans located pyridine ligands. Average Mo? X and Mo? N (pyridine) bonds are; (cation) 2.41, 2.21 Å (A); 2.54, 2.21 Å (B); (anion) 2.44, 2.20 Å (A); 2.58, 2.20 Å (B). Anionic part of the compounds can be oxidised by bromine to trans-MoX₄py₂, which precipitates from the solution. Cation can be isolated from the solution in the form of trans-[MoX₂py₄]Br₃ (X = Cl, Br). The compounds were also characterised by chemical analysis, infrared spectroscopy and conductivity measurements.     

Structures involving unshared electron pair. The Crystal Structures of As(OCOCH3)3 and As2O(OCOCH3)4

As₂O(OCOCH₃)₄, reported now for the first time, was obtained, besides As(OCOCH₃)₃ by dissolving As₂O₃ in acetic anhydride. The crystals of As(OCOCH₃)₃ (A) (monoclinic, space group Cc, Z = 4, a = 9.970(2), b = 13.203(2), c = 8.272(1) Å, β = 117.01(2)°) and of As₂O(OCOCH₃)₄ (B) (monoclinic, space group P2₁/n, Z = 4, a = 13.966(5), b = 8.127(4), c = 12.706(4) Å, β = 95.14(1)°) are built up from discrete molecules defined by chemical formulae As(OCOCH₃)₃ and (CH₃OCO)₂As? O? As(OCOCH₃)₂, respectively. The molecular structure of both compounds is based on the AsO₃ pyramid: in (A) with the As? O bonds of 1.841(6) Å and the O? As? O angle of 89.9(3)° as a mean, in (B) with slightly different values and with the As? O? As angle of 127.7(4)° at the bridging oxygen atom. The additional weak chelating contacts are at the distances As…O from 2.625(9) to 2.745(10) Å in (A) and from 2.72(1) to 2.84(2) in (B). The actual arsenic coordination can be described as very distorted octahedral in (A) and square-pyramidal in (B).     

Die Kristallstruktur des Tetrakis(di-tert.-butylphosphino)diphosphans. [(tBu)2P]2P?P[P(tBu)2]2

The Crystal Structure of Tetrakis(di-tert.-butylphosphino)diphosphane [(tBu)₂P]₂P? P[P(tBu)₂]₂ [(tBu)₂P]₂P? P[P(tBu)₂]₂ 1 obtained at ?20°C from a solution of (tBu)₂P? P=P(Br)tBu₂ forms yellow crystals (regular hexagons). 1 crystallizes monoclinic in the space group C2/c with a = 2145.6pm, b = 1137pm, c = 1696.1pm, β = 110.075° and Z = 4 formula units in the elementary cell. Due to high steric load the bond angles at the tertiary P atoms with δ = 115.7° are significantly larger than those at the primary P atoms with δ = 108.6°.     

[Co(N-(2-Aminoethyl)-1,3-propanediamine)(1,2-diamino-2-methylpropane)Cl][ZnCl4]配合物部分异构体的结构解析

利用过氧化物合成分解法制备得到一新的 [Co(N-(2-Aminoethyl)-1,3 propanediamine)(1,2-diamino-2-methylpropane)Cl]~(2＋)体系配合物,并用柱层析分离得到部分几何异构体。用单晶 X-射线衍射分析方法解析了其中一反式（三元胺仲氮上的氢相对于 Cl）经式异构体的晶体结构,用二维核磁共振技术的同核质子相关 gCOSY及 NOESY谱解析了其中一顺式（三元胺仲氮上的氢相对于 Cl）经式异构体在溶液中的结构。     

ChemInform Abstract: Structures and Bonding of Auropolyboroenes [Au2(B4)xB3]‐, [Au2(B4)xB2]2‐ and [Au2(B4)xB]+(x = 2, 3): Comparison with Dihydride Polyboroenes.

Equilibrium structures of title ions are determined by DFT calculations (TPSS with the τ‐dependent gradient‐corrected functional as implemented in the GAUSSIAN09 code).     

Die Bildung von [(tBu)2P]2P?P[P(tBu)2]2 aus LiP[P(tBu)2]2 und 1,2-Dibromethan. Die Thermolyse von tBu2P?PP(Br)tBu2

[(tBu)₂P]₂P? P[P(tBu)₂]₂ from LiP[P(tBu)₂]₂ and 1,2-Dibromomethane. Pyrolysis of tBu₂P? P?P(Br)tBu₂ All products of the reaction of [tBu₂P]₂PLi 1 with 1,2-dibromoethane 2 were investigated. Already at ?70°C tBu₂P? P?P(Br)tBu₂ 3 as main product and [tBu₂P]₂PBr 4 are formed. Only with an excess of 1 also [tBu₂P]P? P[P(tBu)₂]₂ 5 is obtained. Warming of a pure solution of 3 in toluene from ?70°C to ?30°C leads to 4 , and at 20°C tBu₂PBr and the cyclophosphanes P₄[P(tBu)₂]₄ and P₃[P(tBu)₂]₃ are observed. 5 does not result from 3 , it's rather a byproduct from the reaction of 1 with 4 . Also the ylide 3 and 1 yields 5 .     

Synthese und Struktur von Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octan – Eine neue Käfigverbindung mit dem Sn(P2)3Sn-Gerüst

Synthesis and Structure of Hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane – a New Cage Compound with the Sn(P₂)₃Sn Skeleton The reaction of the diphosphide K₂[(tBuP)₂] 1 with SnCl₄ leads by a redox process mainly to (tBuP)_3,4 and other sideproducts. However, at the same time a threefold [2 + 1]-cyclocondensation reaction takes place yielding the new cage compound hexa-t-butyl-1,4-dichloro-1,4-distanna-2,3,5,6,7,8-hexaphosphabicyclo[2.2.2]octane, ClSn(tBuP? PtBu)₃SnCl 2 . 2 could be obtained in a pure form and characterized ³¹P and ¹¹⁹Sn NMR spectroscopically; 2 was also characterized by a single crystal structure analysis.     

Syntheses and Crystal Structures of [Ni(L)2(NCS)2] and [Co(L)2(NCS)2] (L = Azobis(2-pyridine)

1 INTRODUCTION The synthesis of new organic-inorganic hybrid compounds is a relatively new research area that has developed rapidly in the last several years[1]. Bische- late ligand[2, 3], such as azobis(2-pyridine), is a novel tetradentate ligand expect…     

Synthesis and Crystal Structures of S 2 O 2 Macrocycle L, and its Silver(I) and Platinum(II) Complexes (Where L = 5,8-dioxa-2,11-dithia-[12]-o-cyclophane)

The S₂O₂-donor macrocycle, L(5,8-dioxa-2,11-dithia-[12]-o-cyclophane or 3,4-benzo-1,6-dithia-9,12-dioxocyclo-tetradecane-3-ene) was synthesized by ring closure reaction of 2,2'-(ethylenedioxy)diethanethiol with ,'-dibromo-o-xyleneunder high dilution and crystallized from methanol. The X-ray structure of L has a C₂ axis and is shown to have two S atoms oriented exodentate and two O atoms positionedendodentate to the ring cavity. Reaction of AgNO₃ with L affords monomeric [Ag(L)(NO₃)], (1)in which the Ag atom is in a distorted trigonal plane coordinated by two S atoms in a ring and to one O atom from the NO₃ ^- ion. The behavior of complex 1 in solution was also characterized by NMR titration. Reaction between K₂PtCl₄ and L affords [Pt(L)Cl₂], (2) in which the Pt atom has a distorted square-planar environment, coordinated to two S atoms of Land to two Cl^- ions in a cis arrangement.     

[Co(2,3-tri)(cmen)Cl][ZnCl_4]配合物的合成及其两经式异构体的晶体结构

合成了Co23tricmenClZnCl423tri=N2胺乙基13丙二胺cmen=12二胺基丙烷体系中的部分配合物异构体解析了其中两异构体的晶体结构。其中晶体属单斜晶系空间群P21/ca=1.02112nmb=0.92082nmc=1.95004nmβ=97.9074°V=1.81617nm3Dc=1.803g·cm-3Z=4F000=1000.00μMoKα=29.66cm-1R=0.0317Rw=0.0923晶胞中含4个配合物阳离子4个ZnCl42-阴离子晶体属三斜晶系空间群a=0.9095318nmb=0.96942nmc=1.17712nmα=110.6694°β=92.2384°γ=91.2114°V=0.96973nm3Dc=1.750g·cm-3Z=2F000=520.00μMoKα=27.84cm-1R=0.0365Rw=0.0975晶胞中含2个配合物阳离子2个ZnCl42-阴离子及2个水分子。两异构体中Co3 为六配位其差异仅表现在二元胺cmen中甲基的取向不同。在结构单元中对映体的比例为1∶1。     

[Co4P2(PtBu2)2(CO)8] und [{Co(CO)3}2P4tBu4] aus Co2(CO)8 und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co₄P₂(P^tBu₂)₂(CO)₈] and [{Co(CO)₃}₂P₄^tBu₄] from Co₂(CO)₈ and ^tBu₂P–P=P(Me)^tBu₂ Co₂(CO)₈ reacts with ^tBu₂P–P=P(Me)^tBu₂ yielding the compounds [Co₄P₂(P^tBu₂)₂(CO)₈] ( 1 ) and [{η^2tBu₂P=P–P=P^tBu₂}{Co(CO)₃}₂] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ₂‐bridged by ^tBu₂P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)₃ units is η²‐coordinated to the terminal P₂ units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.     

Reactive E=C(p‐p)π‐Systems. 56 [1] Attempted Preparation of PhE=C(CF3)2 by Reactions of Hexafluoroacetone with PhE(SiMe3)2 (E = As,P)

The chance to prepare sterically and inductively stabilized arsa‐ and phosphaalkenes of the type PhE=C(CF₃)₂ (E = As, P) by reacting phenyl‐bis(trimethylsilyl)‐arsane ( 1 ) and ‐phosphane ( 5 ), respectively, with hexafluoroacetone (HFA) was investigated. The insertion of the carbonyl function in one of the Si–E bonds was found to occur at temperatures between ?78 and 20 °C. The elimination of hexamethyldisiloxane, which in case of acylamides and ketones spontaneously follows the insertion and in case of RE(SiMe₃)–CR′₂(OSiMe₃) at least can be initiated by solid sodium hydroxide as catalyst, turned out to be impossible for the primary products PhE(SiMe₃)–C(CF₃)₂‐OSiMe₃ [E = As ( 2 ), P ( 6 )]. 2 and 6 were characterized by analytical (C, H) and spectroscopic methods (IR, NMR, MS).