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.     

Komplexchemie reaktiver organischer Verbindungen. XLIV. Dimethylcarben- und Acetonazin-Komplexe aus 2-Diazopropan

Organometallic Chemistry of Reactive Organic Compounds. XLIV. Dimethylcarbene and Acetone Azine Complexes from 2-Diazopropane The ether complex of composition (η⁵-C₅H₅)Mn(CO)₂(thf) ( 1 ; thf = tetrahydrofuran) which is prone to substitution of the thf ligand, reacts with 2-diazopropane ( 2 ) at temperatures around 0…5°C (thf solution) to yield the known dimethylcarbene manganese complex 3 as well as the novel acetone azine complex 4 . According to a single crystal X-ray diffraction study, this latter compound belongs to the structures of type (η⁵-C₅H₅)Mn(CO)₂L and exhibits a ketazine ligand that coordinates as a strong σ-donor via one of the nitrogen atoms. The manganese-nitrogen bond length amounting to 206.3(3) pm is much longer than the distance typical of π-acidic nitrogen ligands in analogous complexes.     

Antimon-organo-Verbindungen. VI. Kristallines „Phenylantimon”︁ Bildung und Spaltung mit Natrium bzw. Lithiumbutyl

Organoantimony Compounds. VI. Crystalline Phenyl Antimony. Formation and Cleavage with Sodium and Lithium Butyl, respectively Reactions of C₆H₅SbH₂ with C₆H₅CH ? CH₂, C₆H₅C ? CH and other unsaturated compounds give the corresponding hydrogenated system and phenyl antimony as orange-red crystals and the formula (C₆H₅Sb)₆ · 1 C₆H₆ 1.1 reacts with sodium by cleavage of Sb–Sb bonds forming C₆H₅SbNa₂ and C₆H₅(Na)Sb–Sb(Na)C₆H₅. These stibides are suitable materials to prepare tert. stibines, distibines and cyclic stibines. The cleavage of 1 with butyllithium is a complicated reaction and gives beside other stibides also C₆H₅(C₄H₉)SbLi which can be characterized as (CH₃)₃Si–Sb(C₄H₉)C₆H₅. The ¹H-nmr data of the prepared stibines are discussed.     

Element-Element-Bindungen. VI. Kristallines 2-Chlor-1,3,2-benzoxathiastibol – ein mehrfach verknüpftes Koordinationspolymeres

Element-Element-Bonds. VI. Crystalline 2-Chloro-1,3,2-benzoxathiastibole – a Multiply Linked Coordination Polymer Yellow 2-chloro-1,3,2-benzoxathiastibole 4a first prepared by Anchisi and coworkers [3] from o-hydroxythiophenol and antimony trichloride, crystallizes in the monoclinic space group P2₁/n {a = 1109.9(3); b = 610.5(2); c = 1201.5(2) pm; β = 100.35(2)° at ?120 ± 3°C; Z = 4}. An X-ray structure determination (R = 0.029) shows the molecules to form coordination polymeric layers via Sb…?Cl, Sb…?O and Sb…?η²-arene interactions in the solid. Characteristic structural features are Sb? Cl…?Sb? Cl helices (Sb? Cl…?Sb 119°; Cl? Sb…?Cl 95°) and centrosymmetric, four membered Sb₂O₂-rings (O? Sb…?O 64°; Sb? O…?Sb 116°). The ligands set up a strongly distorted octahedron around the antimony atom: Sb? S 242; Sb? Cl 243; Sb…?Cl 328; Sb? O 201; Sb…?O 287; Sb…?C 338 and 341 pm; S? Sb? O 85°; S? Sb? Cl 94°; O? Sb? Cl 92°.     

Triorganoantimon- und Triorganobismutdisulfonate Kristall- und Molekülstrukturen von (C6H5)3M(O3SC6H5)2 (M = Sb,Bi)

Triorganoantimony and Triorganobismuth Disulfonates. Crystal and Molecular Structure of (C₆H₅)₃M(O₃SC₆H₅)₂(M = Sb, Bi) Triorganoantimony disulfonates R₃Sb(O₃SR′)₂ [R = CH₃ = Me, C₆H₅ = Ph; R′ = Me, CH₂CH₂OH, Ph, 4-CH₃C₆H₄. R = Ph; R′ = 2,4-(NO₂)₂C₆H₃], Me₃Sb(O₃SCF₃)₂ · 2 H₂O and triphenylbismuth disulfonates Ph₃Bi(O₃SR′)₂ [R = Me, CF₃, CH₂CH₂OH, Ph, 4-CH₃C₆H₄, 2,4-(NO₂)₂C₆H₃] have been prepared by reaction of Me₃Sb(OH)₂, (Ph₃SbO)₂, and Ph₃BiCO₃, respectively, with the appropriate sulfonic acids. From vibrational data an ionic structure is inferred for Me₃Sb(O₃SCF₃)₂ · 2 H₂O and Me₃Sb(O₃SCH₂CH₂OH)₂, and a covalent structure for the other compounds with a penta-coordinated central atom with trigonal bipyramidal surrounding (Ph or Me in equatorial, unidentate sulfonate ligands in apical positions). Ph₃M(O₃SPh)₂ (M = Sb, Bi) crystallize monoclinic [space group P2₁/c; M = Sb/Bi: a = 1 611.5(8)/1 557.4(9), b = 987.5(6)/1 072,5(8), c = 1 859.9(9)/1 696.5(9) pm, β = 105.71(5)/96.62(5)°; Z = 4; d(calc.) 1.556/1.781 Mg · m^?3; V_cell = 2 849.2 · 10⁶/2 814.8 · 10⁶ pm³; structure determination from 3 438/3 078 independent reflexions (I ≥ 3σ(I)), R(unweighted) = 0.030/0.029]. M is bonding to three Ph groups in the equational plane [mean distances Sb/Bi? C:210.1(4)/219.1(7) pm] and two sulfonate ligands with O in apical positions [distances Sb? O: 210.6(3), 212.8(2); Bi? O: 227.6(5), 228.0(4) pm]. Weak interaction of M with a second O atom of one sulfonate ligand is inferred from a rather short M? O contact distance [Sb? O: 327.4(4), Bi? O: 312.9(5) pm], and from the distortion of equatorial angles [C? Sb? C: 128.4(2), 119.2(2), 112.2(2); C? Bi? C: 135.9(3), 117.8(3), 106.3(3)°]     

Metallcarbonyl-Synthesen,XIV. Neuartige Vanadium-, Niob- und Tantal-Komplexe mit Wasserstoff-Brücken

Syntheses of Metal Carbonyls, XIV. Novel Vanadium, Niobium, and Tantalum Complexes Having Hydrido Bridges The novel homo- and heterodinuclear organometallic μ-hydrido compounds 3a – c of vanadium, niobium, and tantalum have been synthesized by light-induced reactions of the hydridoniobium complex (η⁵-C₅H₅)₂NbH₃ ( 1 ) with the half-sandwich complexes (η⁵-C₅H₅)M(CO)₄ ( 2a : M = V; 2b : M = Nb; 2c : M = Ta). These compounds have the general composition L_xM – H – Nb(CO)(η⁵-C₅H₅)₂. The formation of the M – H – Nb moieties is a dark-reaction preceded by two photoreactions that are independent from each other elimination of CO from 2a – c and elimination of H₂ from 1 , with the extruded carbon monoxide being transfered to the (η⁵-C₅H₅)₂NbH fragment; subsequent fixation of the species (η⁵-C₅H₅)₂Nb(CO)H thus generated to the photogragments (η⁵-C₅H₅)M(CO)₃ results in donor stabilization of these latter groups. The structural architecture of the derivatives 3a und b was established by X-Ray diffraction. The hydrogen bridges are to be considered as three-center two-electron functions that are responsible for a serious lengthening of the otherwise by at least 40 pm shorter metal-to-metal distances amounting to 371.3 pm in 3a and 373.3 pm in 3b (mean values).     

Die Kristallstrukturen der Triarylzinkate [Mg2Br3(THF)6][ZnPh3] und [MgBr(THF)5][ZnMes3]

Crystal Structures of the Triarylzincates [Mg₂Br₃(THF)₆][ZnPh₃] and [MgBr(THF)₅][ZnMes₃] The title compounds were obtained from reactions of the phosphoraneiminato complex [ZnBr(NPMe₃)]₄ with excess Grignard reagents RMgBr (R = C₆H₅, 2,4,6-(CH₃)₃–C₆H₂) in THF solution. According to X-ray structure determinations the [ZnR₃]^– ions contain zinc atoms which are coordinated in a planar fashion with Zn–C distances of 200.7 pm (R = Ph) and 203.4 pm (R = Mes) in average.     

Übergangsmetall-substituierte vb elementsysteme : VIII. Darstellung und komplexchemisches verhalten von cyclopentadienyl(tricarbonyl)viametall-dimethylstibinen

Starting with the cyclopentadienyl(carbonyl)metal anions [π-C₅H₅(CO)₃M]^? (M = Cr, Mo, W) and (CH₃)₂SbBr, transition metal-substituted stibines of the form π-C₅H₅(CO)₃MSb(CH₃)₂ are obtained. The nucleophilic character of the VB element primarily determines the reactivity of these species, and shows itself in alkyl halide quarternization (a) or ligand exchange on activated metal carbonyl complexes (b). (a) yields the trialkylstibine-substituted metal cations [π-C₅H₅-(CO)₃MSb(CH₃)₂R]X (R = CH₃, CH₂CH=CH₂, CH₂C₆H₅; X = Br, J), (b) leads to the formation of the metal carbonyl derivatives LM(CO)₅, L₂M(CO)₄ (M = Cr, Mo, W), LNi(CO)₃ and LFe(CO)₄ [L = (CH₃)₂SbM(CO)₃-π-C₅H₅] which are the first (CH₃)₂Sb-bridged polynuclear complexes. Phosphorus ylides cause heterolytic cleavage of the antimonytransition metal bond. Transfer of the (CH₃)₂Sb-group to the ylidic carbanion occurs via substitution/transylidation. All new compounds have been fully characterized by means of ¹H NMR, IR and mass spectroscopy     

Untersuchungen am Chlordiphenyl‐ und Tribenzylstiban sowie am Tribenzyldibromstiboran – Molekülstrukturen und Isotypie

Element–Element Bonds. X. Studies of Chloro(diphenyl)stibane, Tribenzylstibane and Tribenzyldibromostiborane – Molecular Structures and Isotypism Chlorodiphenylstibane ( 1 d ) {P2₁/c; Z = 4; a = 1191.8(1); b = 853.4(1); c = 1112.0(1) pm; β = 93.60(1)°; –100 ± 2 °C} crystallizes isotypically with a series of homologous (H₅C₆)₂E–X compounds (E = As, X = Cl, Br, I; E = Sb, X = Br, I); the structure type of tribenzylstibane ( 5 d ) {Pbca; Z = 8; a = 832.1(2); b = 2681.3(5) pm; c = 1600.9(3); –100 ± 3 °C} is already known from tribenzylmethanol, ‐silanol and ‐silane. Tribenzyldibromostiborane ( 6 ) {P2₁/n; Z = 4; a = 938.4(2); b = 2292.4(5); c = 1019.7(2) pm; β = 112.71(1)°; –100 ± 3 °C} does not show an analogous relationship to known structure types. Characteristic mean bond lengths and angles are { 1 d , Sb–Cl 240.9(1), Sb–C 214.0 pm, Cl–Sb–C 93.8°, C–Sb–C 98.6(1)°; 5 d , Sb–C 217.5(3) pm, C–Sb–C 94.9(6)°; 6 , Sb–Br 264.6; Sb–C 217.0(8) pm, Br–Sb–Br 179.4(1)°; C–Sb–C 120°; Br–Sb–C 84.8(2)° to 94.7(2)°}. Stiborane 6 exhibits very weak intermolecular Sb‥Br interactions of 417 pm which, however, affect the molecular conformation in a striking way.     

Tris(2,4,6-trimethylphenyl)antimony dihydroxide; synthesis and reaction with sulfonic acids RSO3H (R = C6H5, CF3). Crystal structure of [2,4,6-(CH3)3C6H2]3SbO · HO3SC6H5

Tris(2,4,6-trimethylphenyl)antimony dihydroxide, Mes₃Sb(OH)₂, which was prepared by oxidation of Mes₃Sb with H₂O₂, has been shown to react with RSO₃H (R = C₆H₅, CF₃) to give the adducts Mes₃SbO · HO₃SR, the first examples of solid hydrogen-bonded adducts of a triorganoantimony oxide and an acid. The crystal structure of Mes₃SbO·HO₃SC₆H₅ has been determined. The three C(mesityl) atoms and the O atom form a distorted tetrahedron around Sb, the distortion by the bulky mesithyl groups being reflected in the CSbC angles (mean: 114.7(3)°) and the CSbO angles: (mean: 103.5(2)°). C₆H₅SO₃H is linked via a short hydrogen bond to O on Sb, with O(1) z^.;O(2) = 256(1) pm. The bond length SbO(1) 189.4(5) pm represents the shortest SbO distance ever reported.     

Molekül- und Kristallstruktur des 1,4-Bis[tris(tetrahydrofuran)lithium]-octaphenyltetrasilans

Molecular and Crystal Structure of 1,4-Bis[tris(tetrahydrofuran)lithium]-octaphenyltetrasilane 1,4-Dilithium-octaphenyltetrasilane prepared from octaphenyl-cyclo-tetrasilane and lithium in tetrahydrofuran (THF) [4], can be isolated from tetrahydrofuran/n-pentane as an adduct with six molecules of tetrahydrofuran per formula unit. The orange-red compound crystallizes in the triclinic space group P1 {a = 1159.6(3); b = 1268.4(2); c = 1367.8(3) pm; α = 92,23(2)° β = 113.79(2)° γ = 111.62(2)° at ?5 ± 3°C; Z = 1}. An x-ray structure determination (R_w = 0.046) shows the existence of a centrosymmetric molecule with an extended planar Li? Si₄? Li unit; either lithium atom is bound to silicon and to the oxygen atoms of three molecules of tetrahydrofuran. Characteristic bond lengths and angles are: Li? Si 271; Si? Si 241 and 243; Si? C 190 to 192 pm; Li? Si? Si 126°; Si? Si? Si 127°. ²⁹Si and ⁷Li n.m.r. measurements at low temperatures indicate the presence of three different adducts.     

Das iso-Tetraphosphan P[P(SiMe3)Me]2[P(SiMe3)2]

H ? C Bond Cleavage in Ferrocene by Organylruthenium Complexes Cp*(Me₃P)₂RuCH₂CMe₃ ( 1 ) reacts at 85°C with ferrocene ( 2 ) by cleavage of one H? C bond in 2 to give CpFe[η⁵-C₅H₄Ru(PMe₃)₂Cp*] ( 3 ) (Cp = η⁵-C₅H₅; Cp* = η⁵-C₅Me₅) and neopentane. The ruthenium atom in 3 has a distorted tetrahedral geometry, the planar Cp ligands in the ferrocenyl fragment are eclipsed. Solutions of 3 in [D₆]benzene or [D₈]THF exhibit H? D exchange of the ferrocenyl protons. In the [D₈]THF molecule only the α-deuterium atoms are exchanged. Reaction pathways for this exchange are discussed.     

Metallcarbonyl-Synthesen. 23. Kristallstruktur und Reaktionsverhalten von Carbonylmetall-Komplexen des Heptamethylindens

Syntheses of Metal Carbonyls. 23. Crystal Structure and Reactivity of Heptamethylindenyl Carbonyl Metal Complexes Reaction of heptamethylindene (C₉(CH₃)₇, 1 ) with Re₂(CO)₁₀ yields [η⁵-C₉(CH₃)₇]Re(CO)₃ ( 2 ), which reacts with NO⁺BF₄^? to form the cationic complex [{η⁵-C₉(CH₃)₇}Re(CO)₂NO]⁺BF₄^? ( 3 ). Irradiation of 2 with UV light in the presence of triethyl phosphite leads to formation of [η⁵-C₉(CH₃)₇]Re(CO)₂[P(OC₂H₅)₃] ( 4 ). Alkylation of (CH₃)₃SnCl with Ind*Li gives [η¹-C₉(CH₃)₇]Sn(CH₃)₃ ( 5 ). All compounds were characterized by spectroscopic methods. The molecular structures of 3 and 5 were determined by single crystal X-ray diffraction ( 3 : P2₁/n (14), a = 1497.7(4) pm, b = 879.0(2) pm, c = 1609.0(4) pm and β = 110.99(2)°, R₁ = 0.038, wR₂ = 0.080; 5 : P2₁/n (14), a = 726.1(1) pm, b = 2930.7(3) pm, c = 930.0(1) pm and β = 112.834(5)°, R₁ = 0.044, R_w = 0.048). Complexes 2 ? 4 exhibit a piano stool configuration with a η⁵-coordinated permethylindenyl ligand (Ind*). Compound 5 displays a η¹ -coordination of the Ind* ligand. Temperature enhancement causes a hapticity change, as observed by NMR spectroscopy.     

[{(η5-C5H4CH3)2YbIII(OC4H8)}(μ2-O)]: Ein neuer Lanthanoid (Ln)-Komplex mit streng linearer LnOLn-Anordnung

Light-green, well-shaped crystals of the new binuclear complex: [{(η⁵-C₅H₄CH₃)₂Yb^III(THF)}₂(μ-O)] (1), incidentally obtained from a solution of (C₅H₄CH₃)₃Yb^III in tetrahydrofuran (THF) in the presence of glyoxal-bis(tert-butylimine), have been subjected to a single-crystal X-ray diffraction study. The crystals are monoclinic, with space group P2₁/c and a 1110.4(2), b 862.3(1), c 1628.0(3) pm; β 104.69(1)°; R = 0.047 (R_w = 0.051). The YbO distance of 201.5(1) pm within the strictly linear YbOYb skeleton belongs to the shortest LnO bonds (Ln = lanthanoid element) so far observed.     

Mixed halide dialkyldithiophosphate derivatives of arsenic(III) and antimony(III)

Mixed chloride dialkyldithiophosphates of arsenic(III) and antimony(III), [(RO)₂PSS]_nMCl_3?n (M = As, Sb; n = 1, 2; R = C₂H₅, n-C₃H₇, i-C₃H₇ and i-C₄H₉) have been synthesized for the first time by the reac metal chlorides with sodium dialkyldithiophosphates or alternatively by co-disproportionation reactions of metal chlorides with metal tris(dialkyldithiophosphates) in different stoichiometric ratios. Mixed halide dialkyl-dithiophosphates of antimony(III) have also been prepared by the cleavage reactions of antimony tris(diisopropyldithiophosphate) with bromine or iodine. Hydrolysis reactions of a few of these compounds have also been studied. The new compounds have been characterized by elemental analyses, molecular weight determinations (cryoscopic) as well as IR and NMR (¹H, ³¹P) data; chelated structures with bidentate dialkyldithiophosphate groups are proposed.     

[Sb(NPPh3)4]+SbF6−: Synthese,Kristallstruktur und 121Sb-Mößbauer-Spektrum

[Sb(NPPh₃)₄]⁺SbF₆^?: Synthesis, Crystal Structure, and ¹²¹Sb Mössbauer Spectrum The title compound as well as the hexachloro antimonate [Sb(NPPh₃)₄]⁺SbCl₆^? have been prepared by the reaction of Me₃SiNPPh₃ with SbF₅ and SbCl₅, respectively, in acetonitrile solutions. The compounds form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy, by ¹²¹Sb Mössbauer spectroscopy, and by crystal structure analyses. A complete crystal structure analysis, however, could be carried out with [Sb(NPPh₃)₄]⁺SbF₆^? only. The compound crystallizes orthorhombically in the space group Pccn with four formula units per unit cell. The structure determination was done with 3 972 observed unique reflections, R = 0.053. Lattice dimensions at 19°C: a = 1 658,6; b = 1 698.9, c = 2 361.9 pm. In the cation [Sb(NPPh₃)₄]⁺ the antimony atom is tetrahedrally coordinated by the four nitrogen atoms of the phosphoraneiminato ligands with extremely short Sb? N bond lengths of 193 pm.     

Zur Reaktivität von Disilylphosphidokomplexen des Eisens und Rutheniums gegenüber 2,4,6-t-Bu3C6H2AsCl2. Bildung und Struktur von Arsaphosphenylkomplexen,Diphosphaarsiranen, Phosphadiarsiranen und 1,2-Diphospha-3,4-diarsetanen

On the Reactivity of Disilylphosphido Complexes of Iron and Ruthenium towards 2,4,6-t-Bu₃C₆H₂AsCl₂. Generation and Structures of Arsaphosphenyl Complexes, Diphospha-ariranes, Phosphadiarsiranes, and 1,2-Diphospha-3,4-diarsetanes The reaction of (η⁵-C₅Me₅)(CO)₂Fe? P(SiMe₃)₂ ( 1a ) with 2,4,6-t-Bu₃C₆H₂AsCl₂ (= Aryl AsCl₂) ( 6 ) leads to the formation of the heterocycles [(η⁵-C₅Me₅)(CO)₂Fe? P]₂As-Aryl ( 7a ), (η⁵-C₅Me₅)(CO)₂Fe? P(As-Aryl)₂ ( 8a ), and [(η⁵-C₅Me₅)(CO)₂Fe? P-As-Aryl]₂( 9a ). The instable arsaphosphenyl complex [(η⁵-C₅Me₅)(CO)₂Fe? P?As-Aryl] can be intercepted as its Cr(CO)₅-adduct 13a . Analogously the ring compounds (η⁵-C₅Me₅)(CO)₂Ru? P]₂(As-Aryl)( 7b ) and (η⁵-C₅Me₅)(CO)₂Ru? P(As-Aryl)₂ ( 8b ) are obtained by treatment of (η⁵-C₅Me₅)(CO)₂Ru? P(SiMe₃)₂ ( 1b ) with 6 . Here again the primarily generated arsaphosphene has to be stabilized by coordination to Cr(CO)₅ which gave E-(η⁵-C₅Me₅)(CO)₂Ru? P[Cr(CO)₅ = As-Aryl ( E-13b ) and its Z-isomer ( Z-13b ). A comparable reaction sequence furnished the phosphaarsenyl complex (η⁵-C₅Me₅)(CO)(PPh)₃Fe? P[Cr(CO)₅] = As-Aryl ( 13c ). The molecular structures of 7a and 9a were elucidated by x-ray diffraction analysis. The most interesting feature of 7a is the AsP₂-triangle, in which the As? P(2) bond length (235,0(2) pm) is slightly elongated with respect to the As? P(1) distance (231,6(1) pm). This effect is presumably due to severe steric interactions at the cis-substituted As? P(2) bond. Molecule 9a displays the picture of a bended 1,2-diphospha-3,4-diarsetane (interplanar angle 137.6°) with its substituents in the all trans-orientation. The As? P and P? P separations are normal whereas the As? As bond (249,7(4) pm) is slightly widened with respect to the calculated value for a single bond (ca 244 pm).     

Darstellung und Struktur von Antimon(III)-tris(thiophosphinaten)

Preparation and Structure of Antimony (III) Tris (thiophosphinates) The title compounds are formed by the reaction of Sb(CH₃COO)₃ with thiophosphinic acids R₂P(?S)OH (R = CH₃ cyclo-C₆H₁₁, C₆H₅). The crystal and molecular structures of Sb((cyclo-C₆H₁₁)₂POS)₃ and Sb((C₆H₅)₂POS)₃ have been determined by single crystal X-ray methods. Sb^III is pyramidally coordinated to the oxygen atoms of the R₂POS ligands through short (primary) bonds with a mean length of 203 pm. The Sb? S distances of the mainly chelating ligands vary between 300 and 320 pm (secondary bonds). The lone electron pair is stereochemically active.     

Mono- und Di-t-butylcyclopentadienyl-Carbonyl-Komplexe des Eisens und Molybdäns. Die Kristallstruktur von [Cp″Mo(Co)2]2 (Cp″ = n5-C5H3t-Bu2-1,3)

Mono- and Di-t-Butylcyclopentadienyl Carbonyl Complexes of Iron and Molybdenum — Crystal Structure of [Cp″Mo(CO)₂]₂ (Cp″ = n⁵-C₅H₃-t-Bu₂-1,3) Cothermolysis of M(CO)_m (M = Fe, m = 5; M = Mo, m = 6) with t-Bu-substituted cyclopentadienyls constitutes a simple synthesis of complexes of the type [Cp*M(CO)_n]₂ (CP* = n⁵-C₅H₃ (t-Bu), R, R = H, t-Bu; M = Fe, Mo; n = 2, 3). Each synthesis has an optimal temperature. The yield of Fe complexes decreases at temperatures above 130°C because of decomposition of the product. Optimal yields of [Cp*Mo(CO)₃]₂ are obtained at 130–140°C, whereas at 160°C complexes of the type [Cp*Mo(CO)₂]₂ with formal Mo? Mo triple bonds are obtained. The structure of the complexes is discussed on the basis of ¹H-, ¹³C-NMR, IR, and mass spectrometry. The structure of [Cp″Mo(CO)₂]₂ (Cp″ = n⁵-C₅H₃t-Bu₂-1,3) was determined by X-ray crystallography at ?95°C. It crystallises in the space group Pbca, with cell constants a = 1808.6(6), b = 1308.5(4), c = 2507.9(9) pm, Z = 8, R = 0.031 for 3794 reflections. The Mo? Mo bond length of 253.3 pm is very long for a formal triple bond. The Cp″? Mo? Mo? Cp″ axis is non-linear.