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 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)°]     

Kristall- und MolekülStruktur von Tetramethyl(dimethylthiophosphinato)-stiboran (CH3)4SbOP(S) (CH3)2

Crystal and Molecular Structure of Tetramethyl(dimethylthiophosphinato)stiborane (CH₃)₄SbOP (S) (CH₃)₂ (CH₃)₄SbOP(S)(CH₃)₂ crystallizes in the triclinic space-group P1 with a = 7.125, b = 9.297, c = 18.861 Å, α = 77.44°, ß = 83.86°, γ = 79.91° and four formula units per cell. Stibonium is distorted trigonal-bipyramidal and phosphorous distorted tetrahedral surrounded. The mean values of bondlengths are: Sb? C_eq = 2.108, Sb? C_ax = 2.147, Sb? O = 2.641, P? C = 1.819, P? O = 1.514, and P? S = 1.987 Å.     

Zur Umsetzung von Kupfer(I)‐ und Kupfer(II)‐Salzen mit P(C6H4CH2NMe2‐2)3 ‐ die Festkörperstrukturen von {[P(C6H4CH2NMe2‐2)3]CuOClO3}ClO4, {[P(C6H4CH2NMe2‐2)3]Cu}ClO4, [P(C6H4CH2NMe2‐2)3]CuONO2 und [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐‐2)]CuONO2

Reaction Behaviour of Copper(I) and Copper(II) Salts Towards P(C₆H₄CH₂NMe₂‐2)₃ ‐ the Solid‐State Structures of {[P(C₆H₄CH₂NMe₂‐2)₃]CuOClO₃}ClO₄, {[P(C₆H₄CH₂NMe₂‐2)₃]Cu}ClO₄, [P(C₆H₄CH₂NMe₂‐2)₃]CuONO₂ and [P(C₆H₄CH₂NMe₂‐2)₂(C₆H₄CH₂NMe₂H⁺NO₃^‐‐2)]CuONO₂ The reaction behaviour of P(C₆H₄CH₂NMe₂‐2)₃ ( 1 ) towards different copper(II) and copper(I) salts of the type CuX₂ ( 2a : X = BF₄, 2b : X = PF₆, 2c : X = ClO₄, 2d : X = NO₃, 2e : X = Cl, 2f : X = Br, 13 : X = O₂CMe) and CuX ( 5a : X = ClO₄, 5b : X = NO₃, 5c : X = Cl, 5d : X = Br) is discussed. Depending on X, the transition metal complexes [P(C₆H₄CH₂NMe₂‐2)₃Cu]X₂ ( 3a : X = BF₄, 3b : X = PF₆), {[P(C₆H₄CH₂NMe₂‐2)₃]CuX}X ( 4 : X = ClO₄, 11a : X = Cl, 11b : X = Br, 14 : X = O₂CMe), {[P(C₆H₄CH₂NMe₂‐2)₃]Cu}ClO₄ ( 6 ), [P(C₆H₄CH₂NMe₂‐2)₃]CuX ( 7a : X = Cl, 7b : X = Br, 10 : X = ONO₂), [P(C₆H₄CH₂NMe₂‐2)₂(C₆H₄CH₂NMe₂H⁺NO₃^‐‐2)]CuONO₂ ( 9 ) and [P(C₆H₄CH₂NMe₂‐2)₃]CuCl}CuCl₂ ( 12 ) are accessible. While in 3a , 3b and 6 the phosphane 1 preferentially acts as tetrapodale ligand, in all other species only the phosphorus atom and two of the three C₆H₄CH₂NMe₂ side‐arms are datively‐bound to the appropriate copper ion. In solution a dynamic behaviour of the latter species is observed. Due to the coordination ability of X in 3a , 3b and 6 non‐coordinating anions X^‐ are present. However, in 4 one of the two perchlorate ions forms a dative oxygen‐copper bond and the second perchlorate ion acts as counter ion to {[P(C₆H₄CH₂NMe₂‐2)₃]CuOClO₃}⁺. In 7 , 9 and 10 the fragments X (X = Cl, Br, ONO₂) form a σ‐bond with the copper(I) ion. The acetate moiety in 14 acts as chelating ligand as it could be shown by IR‐spectroscopic studies. All newly synthesised cationic and neutral copper(I) and copper(II) complexes are representing stable species. Redox processes are involved in the formation of 9 and 12 by reacting 1 with 2 . The solid‐state structures of 4 , 6 , 9 and 10 are reported. In the latter complexes the copper(II) ( 4 ) or copper(I) ion ( 6 , 9 , 10 ) possesses the coordination number 4. This is achieved by the formation of a phosphorus‐ and two nitrogen‐copper‐ ( 4 , 9 , 10 ) or three ( 6 ) nitrogen‐copper dative bonds and a coordinating ( 4 ) or σ‐binding ( 9 , 10 ) ligand X. In 6 all three nitrogen and the phosphorus atoms are coordinatively bound to copper, while X acts as non‐coordinating counter‐ion. Based on this, the respective copper ion occupies a distorted tetrahedral coordination sphere. While in 4 and 10 a free, neutral Me₂NCH₂ side‐arm is present, which rapidly exchanges in solution with the coordinatively‐bound Me₂NCH₂ fragments, this unit is protonated in 10 . NO₃^‐ acts as counter ion to the CH₂NMe₂H⁺ moiety. In all structural characterized complexes 6‐membered boat‐like CuPNC₃ cycles are present.     

Organische Phosphorverbindungen XXXVII. Darstellung und Eigenschaften von Bis-(dialkoxyphosphonyl-methyl)-, Bis-(alkoxyphosphinyl-methyl)-und Bis-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

Bis-chloromethyl-alkyl-and - aryl-phosphine oxides, (CICH₂₎₂P(O)R, which are obtained by reaction of (CICH₂₎₂P(O)Cl with GRIGNARD reagents, undergo a MICHAELIS -ARBUSOV reaction when heated for several hours with trivalent phosphorus esters (phosphites, phosphonites, or phosphinites) at 170–180°C. The reaction affords bis-(dialkyloxyphosphonyl-methyl)-, bis (alkyloxyphosphinyl-methyl)-, and bis-(oxophosphoranyl-methyl)-, -alkyl- or -aryl-phosphine oxides, R(O)P[CH₂P(O)R′R″]₂ R = CH₃, C₂H₅, n-C₈H₁₇, n-C₁₂H₂₅, C₆H₅; R′ and R″ = C₂H₅O, C₄H₉O, C₆H₅, CH₃ in good yields. Conversion of the compounds containing alkyloxy groups to the free acids is achieved by refluxing with conc. HCl. Bis-(dihydroxyphosphonyl-methyl)-dodecylphosphine oxide, n-C₁₂H₂₅(O)P[CH₂P(O) (OH)_2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 4 (two equivalents), pH = 6,9 (one equivalent) and pH = 9,6 (one equivalent). This acid, its disodium salt (m. p. 405–410°) and its tetrasodium salt (m.p. > 460°) are surface active and are excellent chelating agents. The ¹H- and ³¹P-NMR. spectra of all the compounds prepared are discussed.     

Direktsynthese von orthometallierten Ketonen des Typs RCO (o-C6H4)Mn(CO)4−nLn (R = Alkyl- und Arylrest,n = 0, 1, 2, L = Ligand)

Direct Synthesis of Orthometallated Ketones of the Type RCO(o-C₆H₄)Mn(CO)_4?nL_n (R = Alkyl and Aryl Groups, n = 0, 1, 2, L = Ligand) The starting materials of the type RMn(CO)_5?nL_n und (C₆H₅)₂ Hg react to the products of the type RCO(o-C₆H₄)Mn(CO)_4?nL_n[n = 0, R = Ch₃, C₂H₅, C₃H₇, C₆H₅,CH₂; R = C₆H₅, n = 1, L = E(C₆H₅)₃, E = P, As, Sb; R = C₆H₅, n = 2, L = P(OR′)₃, R′ = C₆H₅, CH₃, C₂H₅, C₃H₇]. Steps of their complex reaction pathway are proposed. These orthometallated substances have been characterized by means of ¹H-n.m.r., i.r. and u.v. spectroscopic measurements. The determination of the molecular structure of the two compounds RCO(o-C₆H₄)Mn(CO)₃L [R = C₂H₅, L = CO; R = C₆H₅, L = As(C₆H₅)₃] show that both contain a planar heterocyclic five-membered ring of the type .     

Neue Synthesewege für Organohalogenstibane

New Methods for Synthesis of Organohalogenostibanes Organohalogenostibanes RSbX₂ (R = CH₃, C₆H₅; X = Cl, Br) and R₂SbX (R = C₆H₅; X = Cl) are received in good yields by alkylation or arylation of the corresponding antimony halides with Pb(CH₃)₄, Sn(CH₃)₄, Sb(CH₃)₃, or Sb(C₆H₅)₃. These methods are better than those, described in the literature for preparation of the compounds.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4-fluorbenzolsulfonyl)amin-Dimethylsulfoxid(2/1)

Polysulfonyl Amines. XLVI. Molecular Adducts of Di(organosulfonyl)amines with Dimethyl Sulfoxide and Triphenylphosphine Oxide. X-Ray Structure Determination of Di(4-fluorobenzenesulfonyl)amine-Dimethyl Sulfoxide(2/1) From equimolar solutions of the respective components in CH₂Cl₂/petroleum ether, the following crystalline addition compounds were obtained: (X? C₆H₄SO₂)₂NH …? OS(CH₃)₂, where X = H, 4? CH₃, 4? Cl, 4? Br, 4? I, 4? NO₂ or 3? NO₂; [(4? F? C₆H₄SO₂)₂NH]₂ · (OS(CH)₃)₂ ( 8 ); (4? I? C₆H₄SO₂)₂NH · OP(C₆H₅)₃. A (2/1) complex of (4? F? C₆H₄SO₂)₂NH with OP(C₆H₅)₃ could not be isolated. The solid-state structure of the (2/1) compound 8 is compared with the known structure of the (1/1) complex (CH₃SO₂)₂NH · OS(CH₃)₂. The crystallographic data for 8 at ?95°C are: monoclinic, space group C2/c, a = 2 369.9(13), b = 1 006.8(4), c = 2 772.6(13) pm, β = 110.71(4)°, U = 6.187 nm³, Z = 8. Two N? H …? O hydrogen bonds with N …? O 275 and 280 pm connect the disulfonylamine molecules with the dimethyl sulfoxide molecule. The O atom of the latter has a trigonal-planar environment consisting of the S atom and the two hydrogen bond H atoms.     

Synthese monomerer Silber(I)‐Halogenid‐Komplexe mit T‐förmigem Bau – Kristallstrukturanalyse von [P(C6H4CH2NMe2‐2)3]AgBr

Synthesis of Monomeric T‐Shaped Silver(I) Halide Complexes – Crystal Structure Analysis of [P(C₆H₄CH₂NMe₂‐2)₃]AgBr Treatment of the tetrapodal phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 1 ) with equimolar amounts of the silver(I) halides AgX ( 2 a : X = Cl, 2 b : X = Br) produces in tetrahydrofuran at 25 °C the monomeric silver(I) complexes [P(C₆H₄CH₂NMe₂‐2)₃]AgX with planar coordination at the Ag atoms ( 3 a : X = Cl, 3 b : X = Br) in excellent yields. From complex 3 b a single X‐ray crystal structure analysis was carried out. Mononuclear 3 b crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 14.504(6), b = 11.034(3), c = 17.604(5) Å, β = 102.86(4)°; V = 2746.6(16) ų; Z = 4; 2953 observed unique reflections, R₁ = 0.0805. Complex 3 b consists of monomeric sub‐units with a planar T‐shaped arrangement formed by the atoms Ag1, N1, P1 as well as Br1, whereby the P1–Ag1–Br1 array is almost linear orientated.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

Zur Kenntnis der Organophosphorverbindungen. XV. Darstellung und Reaktionen von Trimethylsilylestern der Phosphinsäuren

On Organophosphorus Compounds. XV. Preparation and Reactions of Trimethylsilyl Esters of Phosphinic Acids Trimethylsilylesters of Phosphinic acids R₂P(X)YSi(CH₃)₃ (R ? CH₃, C₂H₅, C₃H₇, t?C₄H₉, C₆H₅; X, Y ? O, S) were prepared by 7 different methods as in some cases easily hydrolysable but thermally remarkably stable compounds. The properties and some reactions of these substances are reported, their structures confirmed by IR? as well as ¹H- and ³¹P-NMR-spectroscopy. Dimethylsilylen-bis(phosphinic acid esters) were obtained according to \documentclass{article}\pagestyle{empty}\begin{document}$ 2{\rm R}_{2} {\rm P(\rm X)\rm ONH}_{4} + {\rm R}_{\rm 2} {\rm SiCl}_{2} \to 2{\rm E NH}_{4} {\rm Cl + R}_{2} {\rm P(X) - O - SiR}_{2} - {\rm O - P(X)R}_{2} ({\rm R = CH}_{3};{\rm X = O,S}) $\end{document}.     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

Bipy,Phen und P(C6H4CH2NMe2‐2)3 in der Synthese kationischer Silber(I)‐Komplexe; die Festkörperstrukturen von [P(C6H4CH2NMe2‐2)3]AgOTf und [Ag(phen)2]OTf

Bipy, Phen, and P(C₆H₄CH₂NMe₂‐2)₃ in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C₆H₄CH₂NMe₂‐2)₃]AgOTf and [Ag(phen)₂]OTf The reaction of [P(C₆H₄CH₂NMe₂‐2)₃]AgX ( 1a , X = OTf; 1b , X = OClO₃) with equimolar amounts of L^capL ( 2a , L^capL = 2, 2′‐bipyridine, bipy; 2b , L^capL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , L^capL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C₆H₄CH₂NMe₂‐2)₃]Ag(L^capL)}⁺X^— (L^capL = bipy: 3a , X = OTf; 3b , X = ClO₄; L^capL = bipy′: 3c , X = OTf; 3d , X = ClO₄; L^capL = phen: 3e , X = OTf; 3f , X = ClO₄) in which the building blocks L^capL and P(C₆H₄CH₂NMe₂‐2)₃ act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me₂NCH₂ built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 5 ) along with [Ag(phen)₂]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)ų and Z = 4 with 8132 observed unique reflections (R₁ = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)ų and Z = 4 with 6209 observed unique reflections (R₁ = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH₂C_2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion.     

C–H-Aktivierung: Synthese und Eigenschaften von Acetonato(C)acidophthalocyaninato(2–)metallaten(III) von Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumacetonato(C)-azidophthalocyaninato(2–)iridat(III)

C–H-Activation: Syntheses and Properties of Acetonato( C )-acidophthalocyaninato(2–)metallates(III) of Rhodium and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Acetonato( C )azidophthalocyaninato(2–)iridate(III) Phthalocyaninato(2–)metallate(I) of rhodium and iridium reacts with carbonyl substrates like acetone or acetylacetone and halides or pseudohalides forming acetonato(C)- or acetylacetonato(C)acidophthalocyaninato(2–)metallates(III), that are isolated as tetra(n-butyl)ammonium complex salts (ⁿBu₄N)[M(R)(X)pc^2–] (M = Rh, Ir; R = aC, acaC; X = Cl, I, N₃, SCN/NCS). (ⁿBu₄N)[Ir(aC)(N₃)pc^2–] · 0,25(C₂H₅)₂O · 0,5 CH₂Cl₂ crystallizes in the triclinic space group P1 with cell parameters a = 16.267(8) Å, b = 17.938(3) Å, c = 18.335(4) Å, α = 74.77(2)°, β = 73.73(3)°, γ = 84.25(3)°, V = 4954(3) ų, Z = 4. There are two crystallographically independent anions, differing by the orientation of the azido ligand either towards an isoindole group or a N_aza bridge of the phthalocyaninate, while the σ-C bonded acetonate is always oriented towards an isoindole group (gauche and ecliptical configuration). The Ir–C distances are 2.12(1) and 2.14(1) Å. Due to the trans influence of the acetonate-C atom the Ir-azide-N distances of 2.22(1)/2.24(1) Å are longer than expected. The electrochemical properties and the optical, vibrational, and ¹H-NMR spectra are discussed.     

Synthese und strukturelle Studien von Aluminiumdialkylaminen und ‐amiden: N‐Chiralität von (CH3)3AlNHRR′ und cis‐trans‐Isomerie an X2AlNRR′ (X = CH3, Cl,H)

Synthesis and Structural Studies of Aluminum Dialkylamines and Dialkylamides: N‐Chirality of (CH₃)₃AlNHRR′ and cis‐trans ‐Isomerism at X₂AlNRR′ (X = CH₃, Cl, H) Aluminum dialkylamines and dialkylamides were prepared from Al(CH₃)₃ and NH(CH₃)R′ (R′: –C₂H₅, –^tC₄H₉) and characterized by elemental analyses, ¹H‐, ¹³C‐, and ²⁷Al‐NMR spectroscopy. The crystal structures of [(CH₃)₂AlN(CH₃)(–^tC₄H₉)]₂ ( IV ), [Cl₂AlN(CH₃)(C₂H₅)]₂ ( V ), and [H₂AlN(CH₃)(C₂H₅)]_∞ ( VI‐trans and VI‐cis ) are discussed.     

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     

Synthesis,characterization and in vitro antitumor activity of some arylantimony ferrocenecarboxylates and crystal structures of C5H5FeC5H4CO2SbPh4 and (C5H5FeC5H4CO2)2Sb(4‐CH3C6H4)3

A series of arylantimony ferrocenecarboxylates with the formula (C₅H₅FeC₅H₄CO₂)_nSbAr_(5?n) (n = 1, 2; Ar = C₆H₅, 4‐CH₃C₆H₄, 3‐CH₃C₆H₄, 2‐CH₃C₆H₄, 4‐ClC₆H₄, 4‐FC₆H₄) were synthesized and characterized by elemental analysis, IR, ¹H NMR and mass spectra. The crystal structures of (C₅H₅FeC₅H₄CO₂)₂Sb(4‐CH₃C₆H₄)₃ and C₅H₅FeC₅H₄CO₂SbPh₄ were determined by X‐ray diffraction. Four human neoplastic cell lines (HL‐60, Bel‐7402, KB and Hela) were used to screen these compounds. The results indicate that these compounds at 10 µM show certain in vitro antitumor activities. Copyright © 2003 John Wiley & Sons, Ltd.     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.     

New Dinuclear Ru2(CO)4 Sawhorse‐Type Complexes Containing Bridging Carboxylato Ligands

The thermal reaction of Ru₃(CO)₁₂ with ethacrynic acid, 4‐[bis(2‐chlorethyl)amino]benzenebutanoic acid (chlorambucil), or 4‐phenylbutyric acid in refluxing solvents, followed by addition of two‐electron donor ligands (L), gives the diruthenium complexes Ru₂(CO)₄(O₂CR)₂L₂ ( 1 : R = CH₂O‐C₆H₂Cl₂‐COC(CH₂)C₂H₅, L = C₅H₅N; 2 : R = CH₂O‐C₆H₂Cl₂‐COC(CH₂)C₂H₅, L = PPh₃; 3 : R = C₃H₆‐C₆H₄‐N(C₂H₄‐Cl)₂, L = C₅H₅N; 4 : R = C₃H₆‐C₆H₄‐N(C₂H₄‐Cl)₂, L = PPh₃; 5 : R = C₃H₆‐C₆H₅, L = C₅H₅N; 6 : R = C₃H₆‐C₆H₅, L = PPh₃). The single‐crystal structure analyses of 2 , 3 , 5 and 6 reveal a dinuclear Ru₂(CO)₄ sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two L ligands occupy the axial positions of the diruthenium unit.