Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].     

Triorganoantimon- und Triorganobismutderivate von Carbonsäuren fünfgliedriger Heterocyclen Kristall- und Molekülstruktur von (C6H5)3Sb(O2C-2-C4H3S)2

Inhaltsübersicht. Triorganoantimon- und Triorganobismutdicarboxylate R₃M[O₂C(CH₂)ⁿ-2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) wurden durch Reaktionen von R₃Sb(OH)₂ (R = CH₃, C₆H₁₁, 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) bzw. R₃BiCO₃ mit den entsprechenden fünfgliedrigen heterocyclischen Carbonsäuren 2-C₄H₃X(CH₂)_nCOOH dargestellt. Auf der Basis schwingungsspektroskopischer Daten wird für alle Verbindungen eine trigonal bipyramidale Umgebung vom M (zwei O-Atome von einzähnigen Carboxylatliganden in den apikalen, drei C-Atome von R in den äquatorialen Positionen) vorgeschlagen, ferner eine schwache Wechselwirkung zwischen O(=C) jeder Carboxylatgruppe und M. Die Kristallstrukturbestimmung von (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₃ stützt diesen Vorschlag. Die Verbindung kristallisiert triklin [Raumgruppe P$1; a = 891,8(14), b = 1058,2(12), c = 1435,6(9) pm, α = 68,53(8), β = 85,47(9), γ = 85,99(11)°; Z = 2; d(ber.) = 1,607 Mg m^–3; V(Zelle) = 1255,6 ų; Strukturbestimmung anhand von 3947 unabhängigen Reflexen (F_o > 3σ(F²_o)), R(ungewichtet) = 0,037]. Sb bindet drei C₆H₅-Gruppen in der äquatorialen Ebene [mittlerer Abstand Sb–C: 211,1(5)pm] und zwei einzähnige Carboxylatliganden in den apikalen Positionen einer verzerrten trigonalen Bipyramide [mittlerer Abstand Sb–O: 212,0(4) pm]. Aus den relativ kurzen Sb – O(=C)-Abständen [274,4(4) und 294,9(4) pm] und aus der Aufweitung des dem O(=C)-Atom nächsten äquatorialen C–Sb–C-Winkels auf 145,9(2)° [andere C-Sb-C-Winkel: 104,4(2), 109,5(2)°] wird auf schwache Sb–O(=C)-Koordination geschlossen. Schließlich wird eine Korrelation zwischen dem (+, –)I-Effekt des Organoliganden R an M (M = Sb, Bi) und der Stärke der M–O(=C)-Koordination in den Dicarboxylaten R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ vorgeschlagen. Triorganoanümony and Triorganobismuth Derivatives of Carbonic Acids of Five-membered Heterocycles. Crystal and Molecular Structure of (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₂ Triorganoantimony- and triorganobismuth dicarboxylates R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) have been prepared by reaction of R₃Sb(OH)₂ (R = CH₃, C₆H₁₁; 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) or R₃BiCO₃ with the appropriate five-membered heterocyclic carboxylic acid. From vibrational data for all compounds a trigonal bipyramidal environment around M (two O atoms of unidendate carboxylate ligands in apical, three C atoms (of R) in equatorial positions) is proposed and also an additional weak interaction of O(=C) of each carboxylate group and M. The crystal structure determination of Ph₃Sb(O₂C–2-C₄H₃S)₂ gives additional prove to this proposal. It crystallizes triclinic [space group P$1; a = 891.8(14), b = 1058.2(12), c = 1435.6(9) pm, α = 68.53(8), β = 85.47(9), γ = 85.99(11)°; Z = 2; d(calc.) = 1.607 Mg m^–3; V_cell = 1255.6 ų; structure determination from 3 947 independent reflexions (F_o > 3σ(F²_o)), R(unweighted) = 0.037]. Sb is bonding to three C₆H₅ groups in the equatorial plane [mean distance Sb–C: 211.1(5) pm] and two unidentate carboxylate ligands in the apical positions of a distorted trigonal bipyramid [mean distance Sb–O: 212.0(4) pm]. From the relatively short Sb–O(=C) distances [274.4(4) and 294.9(4) pm] and from the enlarged value of the equatorial C–Sb–C angle next to the O(=C) atom [145.9(2)°; other C–Sb–C angles: 104.4(2), 109.5(2)°] additional weak Sb–O(=C) coordination is inferred. Finally a correlation between the (+, –) I-effect of the organic ligands It at M and the strength of the M–O = C interaction is suggested.     

Kristall- und MolekülStruktur von 2(C6H5)3AsO · H2SeO3

Crystal and Molecular Structure of 2(C₆H₅)₃AsO · H₂SeO₃ 2(C₆H₅)₃AsO · H₂SeO₃ crystallizes in the orthorhombic space group Fdd2—C_2v¹⁹, with a = 20.472(9), b = 32.747(1) and c = 10.008(8) Å and Z = 8; d (calc./obs.) = 1.52₇/1.52 g · cm^?3. The structure has been determined from 808 independent reflections by Patterson- and Fouriersyntheses, and has been refined by least squares methods to R = 0.056. In the compound two (C₆H₅)₃AsO-units and one selenite group are linked by short H-bonds [O …? H …? O-distance 2.48(4) resp. 2.35(4) Å]. The As? O-distances are 1.64(9), the Se? O-distances are 1.69(3), 1.83(3), resp. 1.76(3) Å.     

Darstellung,Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrochlorid (C6H5)3PO · HCl

On Phosphazo Compounds from Nitriles. IV. The Reaction of Tri, Di, and Monochloroacetonitrile with [Cl₃P?N? PCl₃]Cl. Improved Preparation of [Cl₃P?N? PCl₃]Cl Trichloroacetonitrile reacts with P₂NCl₇ to give Cl₃C? CCl₂? N?PCl₂? N?PCl₃ I , dichloroacetonitrile to give Cl₂C?CCl? N?PCl₂? N?PCl₃ II , and chloroacetonitrile to give the ring compound III . Preparation, n.m.r. and mass spectra of the new compounds are described. The mechanism of formation is discussed. An improved procedure for the preparation of P₂NCl₇ is given.     

Darstellung sowie Kristall- und Molekülstruktur von 2 (C6H5)3PO · (COOH)2

Preparation, Crystal and Molecular Structure of 2 (C₆H₅)₃PO · (COOH)₂ 2(C₆H₅)₃PO · (COOH)₂ crystallizes from a solution of oxalic acid and (C₆H₅)₃PO in methanol. Crystal data: space group P2₁/c (monoclinic) with a = 907.4(2), b = 1035.4(3), c = 1797.9(8) pm, β = 75.20(1)° and Z = 2; d (calc./obs.) = 1.27/1.31 g cm^?;3; V_cell = 1633.1 × 10⁶ pm³. The structure was determined by direct methods from 3006 independent reflections and has been refined by full matrix least squares to R = 0.049. In the compound one molecule of trans-oxalic acid and two symmetrically dependent (C₆H₅)₃PO units are linked by short O…?H–O bridges distances and angles see above.     

Darstellung sowie Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrogenfluorid, (C6H5)3PO · HF

Preparation, Crystal and Molecular Structure of Triphenylphosphineoxide Hydrogen - fluoride (C₆H₅)₃PO · HF (C₆H₅)₃PO · HF was prepared from hydrofluoric acid (40%) and (C₆H₅)₃PO in benzene. It crystallizes in the monoclinic space group P2₁/c with a = 1 032.8(3), b = 1 051.0(7), c = 1695.5(2) pm, β = 121.95(2)° and Z = 4; d (calc./obs.) 1.27/1.26 g ° cm^?3. The structure was determined by direct methods from 2 709 independent reflections and has been refined by full matrix least squares methods to R = 0.049. In the compound HF and (C₆H₅)₃PO are linked by a short H-bond. Some distances: O? F 238.4(5), O? H 142.3, H? F 99.8, P? O 149.5(4) pm. Angle O? H? F 159.8°.     

Die Kristall- und Molekülstrukturen von (Me2SiNCN)4 (1) und Me3SiNCNSiMe3 (2)

Crystal and Molecular Structures of (Me₂SiNCN)₄ (1) and Me₃SiNCNSiMe₃ (2) Synthesis, spectroscopic characterization (NMR, IR, Raman and MS) and crystal structure of the novel compound 1 are described. The molecules form almost planar 16 membered rings with four SiMe₂-groups connected to four NCN groups. The corresponding compound 2 exhibits a phase transition from the HT phase 2a to the LT phase 2b at 131 K. Consecutive X-ray structure determinations of the molecular structures of both modifications were performed on a crystal, grown in situ on the diffractometer at 231 K.     

Neutrale Thiolate und ein Iodidthiolat von Antimon(III). Die Kristallstrukturen von Sb(SC6H5)3, Sb(SC6H2Me3-2,4,6)3 und SbI(SC6H2Me3-2,4,6)2

Neutral Thiolates and a Iodothiolate of Antimony(III). Crystal Structures of Sb(SC₆H₅)₃, Sb(SC₆H₂Me₃-2,4,6)₃, and SbI(SC₆H₂Me₃-2,4,6)₂ The crystal structures of Sb(SC₆H₅)₃ ( 1 ), Sb(SC₆ · H₂Me₃-2,4,6)₃ ( 2 ), and the novel compound SbI(SC₆H₂Me₃-2,4,6)₂ ( 3 ) have been determined by X-ray crystallography. In addition to the expected trigonal pyramidal coordination of antimony intermolecular interactions are observed for 1 (Sb … O: 363.3 pm) and 3 (Sb … S: 2 × 369.4 pm) but not for 2 . The reasons for these differences are discussed.     

Synthese und Kristallstrukturen der Bismutchalkogenolate Bi(SC6H5)3, Bi(SeC6H5)3 und Bi(S‐4‐CH3C6H4)3

Synthesis and Crystal Structures of Bismuth Chalcogenolato Compounds Bi(SC₆H₅)₃, Bi(SeC₆H₅)₃, and Bi(S‐4‐CH₃C₆H₄)₃ Bismuth(III) acetate reacts with thiophenol in ethyl alcohol at 80 °C to yield Bi(SC₆H₅)₃ ( 1 ). Slow cool down of the deep yellow mixture lead to the formation of orange crystals of 1 . The homotype phenylselenolato compound of bismuth Bi(SeC₆H₅)₃ ( 2 ) has been prepared by the reaction of BiX₃ (X = Cl, Br) with Se(C₆H₅)SiMe₃ in diethyl ether. In the same way as Bi(SC₆H₅)₃ ( 1 ) the reaction between bismuth(III) acetate and 4‐tolulenethiole results in red crystals of Bi(S‐4‐CH₃C₆H₄)₃ ( 3 ). In consideration of three longer Bi–E distances (intermolecular interactions, E = S; Se) the Bi(EPh)₃ molecules form via face‐linked octahedra 1‐dimensional chains in the crystal lattice, while for 3 the 1‐dimensional chain is formed by face‐linked trigonal prisma. We reported herein the synthesis and structures of Bi(SC₆H₅)₃ ( 1 ), Bi(SeC₆H₅)₃ ( 2 ), and Bi(S‐4‐CH₃C₆H₄)₃ ( 3 ).     

Die Kristall- und Molekülstrukturen von Chlorotrispyridinium-bis-(tetrachloroaluminat(III)) und einer weiteren Modifikation von Pyridiniumchlorid

Crystal- and Molecular Structures of Chlorotrispyridinium-bis-(tetrachloroaluminate(III)) and a New Modification of Pyridinium Chloride The compounds PyHCl and ((PyH)₃Cl)(AlCl₄)₂ are formed by hydrolysis during the synthesis of adducts in the system AlCl₃/pyridine. The second room temperature modification of PyHCl crystallizes in the space group P2₁/c with the lattice constants a = 847.9(3), b = 1770.2(3), c = 801.9(3) pm, β = 95.23(3)°, Z = 8. The atomic parameters were refined from 4471 measured intensities to R(F) = 6,9%. The N? Cl distances are 306.8(7) and 311.0(8) pm. The unit cell of ((PyH)₃Cl)(AlCl₄)₂ is orthorhombic (space group Pbca) and has the lattice constants a = 1306.3(4), b = 1589.4(4), c = 2708.6(7) pm, Z = 8. The crystal structure was refined from 7226 measured intensities to R(F) = 6.7%. The cation shows three pyridinium ions to have NH…?Cl hydrogen bonds to a central positioned chloride ion with N? Cl distances of 301.4(7), 305(1) and 306(1) pm.     

Die Kristall- und MolekülStruktur von (S4N3)2SbCI5

The structure of (S₄N₃)₂SbCI₅ has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P2₁/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S₄N-rings retained their planar shape.     

Die Kristall- und Molekülstruktur von CuBr · (C2H5)4P2 (monokline Form)

Crystal and Molecular Structure of CuBr · (C₂H₅)₄P₂ (Monoclinic Form) The crystal structure of the copper(I) complex CuBr · (C₂H₅)₄P₂ has been determined by X-ray structure analysis. The substance crystallizes monoclinic, space group C–P2₁/n with a = 10.78, b = 15.74, c = 7.54 Å, β = 84.6° and 4 formula units in the unit cell. The structure was solved by conventional heavy atom methods and has been refined to a final R-value of 0.14. The structure is characterized by continous chains, the copper atoms are tetrahedrally coordinated and linked together by alternating double bridges of two bromine atoms and two biphosphine molecues, respectively.     

Beiträge zur Chemie des Schwefels. 114. Kristall- und Molekülstrukturen vom Hexathiepan (S6CH2), Pentathian (S5CH2) und Dibenzylpentathian (S5C(CH2C6H5)2)

Contributions to the Chemistry of Sulfur. 114. Crystal and Molecular Structures of Hexathiepane (S₆CH₂), Pentathiane (S₅CH₂), and Dibenzylpentathiane (S₅C (CH₂C₆H₅)₂) The crystal and molecular structures of hexathiepane 1 , pentathiane 2 and dibenzylpentathiane 3 were determined by single crystal X-ray structure analyses. 1 : Monoclinic space group P2₁/c; a = 7.694(4), b = 7.668(4), c = 12.367(6) Å, β = 108.9(1)°; Z = 4, d_calc. = 1.986 g/cm₃. The seven-membered heterocycle exists in twist-conformation. 2 : Monoclinic space group C2/c; a = 10.990(5), b = 6.872(4), c = 15.507(6) Å, β = 94.1(1)°; Z = 8, d_calc. = 1.982 g/cm₃. The six-membered heterocycle exists in chair-conformation. 3 : Monoclinic space group P2₁/c; a = 12.907(8), b = 13.611(8), c = 9.408(6) Å, β = 98.9(1)°; Z = 4, d_calc. = 1.442 g/cm₃. 3 is analogous to 2 a six-membered heterocycle with chair-conformation. The benzylic groups are distorted to each other. Bond lengths, bond angles, and dihedral angles of the heterocyclic sulfur rings arc discussed, especially with regard to a comparison with cyclohexasulfur, cycloheptasulfur. and cyclooctasulfur.     

Die Kristall- und Molekülstruktur von (CH3)2SnSAB (SAB = Dianion von 2-Hydroxy-N-(2-hydroxybenzyliden)-anilin)

Crystal and Molecular Structure of (CH₃)₂SnSAB. (SAB = Dianion of 2-Hydroxy-N-(2-hydroxybenzylidene)-aniline) (CH₃)₂SnSAB, C₁₅H₁₅NO₂Sn (SAB = tridentate dianion of 2-hydroxy-N-(2-hydroxybenzylidene)-aniline in SCHIFF base form) crystallizes in the space group Pben (D) with a = 19.271(5), b = 10.508(2), c = 13.379(1) Å and Z = 8. The structure has been solved using 1307 symmetrical independent reflections and applying the heavy atom method; the position of all atoms, except the H atoms, has been determined. As interatomic distances have been found: Sn? C: 2.117(14), Sn? O:2.112(9), Sn? N:2.229(11) N? C 10 (phenyl group II): 1.462(16), C9-N (SCHIFF base bridging group): 1.257(18), C 9? C8 (phenyl group I): 1.441(18) Å; mean C? C distances in the phenyl groups: 1.403(18) Å. Two molecules at a time have a centre of symmetry and weakly coordinate through two loose Sn? O bridges (intermolecular Sn? O distance: 2.881(8) Å). The individual molecules essentially form a distorted trigonal bipyramid with N and both methyl-C atoms in the equatorial plane; ? CSnC = 138.52(50)°; ? OSnO = 158.58(35)°.     

三核过渡金属配合物〔M_3~ⅢO(OOCR)_6L_3〕 (M=Cr,Fe,Mn;R=CH_3,C_2H_5,CH_2NH_2;L=C_5H_5N,H_2O)的~1H NMR性质

采用１ＨＮＭＲ谱研究了通式为〔Ｍ３ⅢＯ（ＯＯＣＲ）６Ｌ３〕＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁交换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表明,其１Ｈ各向同性位移主要由接触作用贡献     

Synthese und Molekülstruktur von meso-(1,2,3-Tricyclohexyltriphosphan-1,3-diyl)zirkonocen(IV), Cp2 (Cp = η5−C5H5, Cy = C6H11)

Synthesis and Crystal Structure of meso-(1,2,3-Tricyclohexyltriphosphane-1,3-diyl)zirconocene(IV), Cp₂ (Cp = η⁵?C₅H₅, Cy = C₆H₁₁) Cp₂ZrCl₂ reacts with Li(THF)₂PHCy (Cy = C₆H₁₁) to yield the metallacyclic compound Cp₂ 1. , The ³¹P{¹H} NMR spectrum of 1 , shows a coupling pattern for an A₂X system, indicating the presence of only the meso-forms in solution, which are also present in the solid state. 1 , crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 12.984(8), b = 9.241(7), c = 23.05(1) Å, β = 93.48(4)°, V = 2760.1 ų and four formula units in the unit cell (2718 independent observed reflections, R = 7.3%). The central ZrP₃ ring in 1 , is almost planar. The Zr? P bond lengths of 2.618(4) and 2.628(4) Å are nearly identical.     

Über die Reaktionen von CH2=P(NMe2)3 mit Fe(CO)5, Cr(CO)6 und CS2; Molekülstrukturen von [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3] und (CO)4Fe=C(OMe)CH=P(NMe2)3

The Reactions of CH₂=P(NMe₂)₃ with Fe(CO)₅, Cr(CO)₆, and CS₂; Molecular Structures of [MeP(NMe₂)₃][(CO)₅CrC(O)CH=P(NMe₂)₃], and (CO)₄Fe=C(OMe)CH=P(NMe₂)₃ The ylide CH₂=P(NMe₂)₃ ( 1 ) reacts with several binary transition metal carbonyls M(CO)_x to produce the corresponding salt like compounds [MeP(NMe₂)₃][(CO)_x–1MC(O)CH=P(NMe₂)₃] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS₂ leads to the salt [MeP(NMe₂)₃][SC(S)CH=P(NMe₂)₃] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe₂)₃]₂[Fe₂(CO)₈] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO₃CF₃ produces the related carbene complexes (CO)_x–1M=C(OMe)CH=P(NMe₂)₃ ( 5 ) and ( 6 ); the reaction of 3 with Me₃SiCl results in the formation of the carbene complex (CO)₄Fe=C(OSiMe₃)CH=P(NMe₂)₃ ( 7 ). 4 crystallizes in the space group P2₁2₁2₁ (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P2₁/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (¹H, ¹³C, ³¹P) and IR spectroscopy.     

Beiträge zur Chemie des Phosphors. 66. Kristall- und Molekülstrukturen von 1,2,3,4-Tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphan, (PC6H5)4CH2, und 1,4-Dithio-1,2,3,4-tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphan, (PC6H5)4CH2S2

Contributions to the Chemistry of Phosphorus. 66. Crystal and Molecular Structure of 1,2,3,4-Tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane, (PC₆H₅)₄CH₂, and 1,4-Dithio-1,2,3,4-tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane, (PC₆H₅)₄CH₂S₂ The following results were achieved by X-ray structure analyses of 1,2,3,4-Tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane 1 and 1,4-Dithio-1,2,3,4-tetraphenyl-cyclo-5-carba-1,2,3,4-tetraphosphane 2 :

• crystallises in the monoclinic space group Cc with a = 22.272, b = 13.726, c = 7.492 Å, β = 96.82° and Z = 4. The P₄C-ring has an envelope conformation. The phenyl groups are arranged alternately on both sides of the ring.
• forms triclinic crystals, space group P1 , with a = 10.900, b = 10.663, c = 12.233 Å, α = 106.26, β = 100.04, γ = 70.65°, Z = 2. The P₄C-ring has twist conformation, the carbon atom lies almost in the mean plane of the ring. The sulfur atoms are bonded in exo position to the phosphorus atoms neighbouring the carbon atom and in trans position to each other.

     

Darstellung,Eigenschaften und Molekülstrukturen von Alkylaluminiumaminoalkoxidchloriden

Synthesis, Properties, and Molecular Structures of Alkylaluminium Aminoalkoxide Chlorides Alkylaluminium aminoalkoxide chlorides [R(Cl)AlOR*] 1 – 3 have been obtained from the reaction of dialkyl aluminium chlorides R₂AlCl with the respective aminoalkohol HOR* ( 1 : R = Et, OR* = dimethylamino‐1‐propanol; 2 : R = Me, OR* = (+);(–)‐dimethylamino‐2‐propanol; 3 : R = Me, OR* = (S)‐N‐methyl‐2‐pyrrolidinyl‐methanol). The reaction between dimethylaluminium chloride and (S)‐α, α‐diphenyl‐2‐pyrrolidinyl‐methanol (OR* = Dpm) yielded, by contrast, the ionic {[MeAl(OR*)₂AlMe₂]⁺ [MeAlCl₃]^–} complex ( 4 ). 1 – 4 have been characterised by ¹H, ¹³C and ²⁷Al‐NMR spectroscopy. Crystal structures of 1 and of the 1 : 1 solvate of 4 with Et₂O have been determined by X‐ray methods and the absolute structure of 4 was confirmed by refinement of the Flack‐parameter. The dimeric molecules of 1 are composed of two chelating rings linked via an almost planar Al₂O₂ unit and pentacoordination is observed about aluminium. In contrast, each of the two crystallographically independent cation molecules of 4 contains one four‐ and and one five‐coordinate metal centre.