Komplexchemie polyfunktioneller Liganden. XXX. Komplexe des Tetrakis(diphenyl-dichlor-phosphoranomethyl)-methan mit FeCl3, SnCl4 und SbCl5

Complex Chemistry of Polyfunctional Ligands. XXX. Complexes of the Tetrakis(diphenyl-dichloro-phosphoranmethyl)methane with FeCl₃, SnCl₄, and SbCl₅ The reaction of C[CH₂P(C₆H₅)₂Cl₂]₄ and FeCl₃ in the 1:4 stoichiometric quantities results in the formation of the tetraphosphonium salt A and the in 1:2 ratio the spirocyclic compound B has been formed. Coincident with the synthesis of B CH₃CN has been chlorinated to some extend. Surprisingly C[CH₂P(C₆H)₂Cl₂]₄ and SnCl₄ yields the much largely non ionic 1:2 adduct C[CH₂P(C₆H₅)₂Cl₂]₄ · 2 SnCL₄, whereas SbCl₅ reacts to the expected salt C[CH₂P(C₆H₅)₂Cl SbCl₆]₄.     

l-Hydroxo/Alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimon(V)]Verbindungen. Zweikernige Antimon(V)-Komplexe mit Sulfonatgruppen als überbrückenden Liganden

l-Hydroxo/alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimony(V)] Compounds. Binuclear Antimony(V) Complexes with Sulfonate Groups as bridging Ligands Sulfonic acids react with antimony(V) chloride and water and water/alcohol resp. dependent of the molar ratios yielding Cl₃SbO(OH)(O₂S(O)CH₃)SbCl₃ ( 1 ), Cl₃SbO(OH)· (O₂S(O)CF₃)SbCl₃ ( 3 ) the monohydrate Cl₃SbO(OH)· (O₂S(O)CH₃)SbCl₃·H₂O ( 2 ) and the compounds Cl₃SbO(OR')(O₂S(O)CF₃)SbCl₃ ( 4 : R'=CH₃; 5 : R'=C₂H₅) and Cl₃SbO(OCH₃)(O₂S(O)C₂H₅)SbCl₃ ( 6 ) resp. The crystal and molecular structures of 1 to 3 , 5 and 6 are determined. 1 and 3 are associated by hydrogen bonds to dimers and crystallize monoclinic ( 1 : P2₁/c; 3 : P2₁/n). 2 is a hydroxonium salt H₃O⁺[Cl₃SbO₂(O₂S(O)CH₃)SbCl₃]^– with strong hydrogen bonds between cations and anions and crystallizes triclinic (P1). 5 and 6 crystallize monoclinic ( 5 : P2₁/m; 6 : P2₁/c). In 1 and 3 to 6 there is an intramolecular reorientation or an intermolecular exchange of protons and R' groups in solution. The NMR spectra are discussed.     

Organic phosphorus compounds : LXXI. Preparation,properties, and structure of bis(aminomethyl)phosphinic acid, (H2NCH2)2P(O)OH

Bis(aminomethyl)phosphinic acid, (H₂NCH₂)₂P(O)OH · HCl, was prepared by debenzylation of (C₆H₅CH₂NHCH₂)₂P(O)OH · HCl with hydrogen using 5% Pd on C as catalyst, and from bis(t-butylaminomethyl)phosphinic acid, (t-C₄H₉NHCH₂)₂P(O)OH, by isobutylene elimination in concentrated aqueous hydrobromic acid at 175°C in sealed tube. Interaction of bis(chloromethyl)phosphinic acid with ammonia in an autoclave produced methylaminomethylphosphinic acid, CH₃NHCH₂P(O)(OH)₂. A mechanism for the formation of this product is proposed. Several derivatives of (H₂NCH₂)P(O)OH such as (RNHCH₂)₂P(O)OH, R = C₆H₅CO, CICH₂CO, [H₂NHNC(=NH)NHCH₂]₂P(O)OH and [(CH₃)₃SiNHCH₂]₂P(O)OSi(CH₃)₃ were prepared.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Wasserstoffbrückenbindungen in zweikernigen μ-Hydroxobis[trichloroantimon(V)]-Komplexen mit Phosphatbzw. Phosphonatgruppen als überbrückende Liganden

Hydrogen Bonds in Binuclear μ-Hydroxo-bis[trichloroantimony(V)] Complexes with Phosphate or Phosphonate Groups as Bridging Ligands Benzylphosphonic acid monoalkylesters react with antimony(V) chloride and water to yield Cl₃SbO(OH)[(C₆H₅CH₂)RPO₂]SbCl₃ · H₂O ( 1 : R = OCH₃; 2 : R = OC₂H₅). With difluoro phosphoric acid only Cl₃SbO(OH)(F₂PO₂)SbCl₃ ( 3 ) can be isolated. The crystal and molecular structures of 1 to 3 were determined. 1 and 2 both crystallizing orthorhombic in the space group Pnma are hydroxonium salts H₃O⁺[Cl₃SbO₂((C₆H₅CH₂)RPO₂)SbCl₃]^–. Strong hydrogen bridges link cations and anions to chains. One of the hydrogen atoms of the cation makes a weak but important OH/π interaction to the para C atom of the benzyl group. In 3 (monoclinic, P2₁/n) the molecules are connected by hydrogen bridges to fourfold δ and helices λ. In solution there is a rapid intermolecular exchange of protons. IR and NMR data are communicated and briefly discussed.     

Darstellung,Redox-Verhalten und Strukturen einkerniger „einfacher”︁ Mono- und Dinitrosyl-Komplexe des Molybdäns mit Hydroxylamido(−1)-, Oximato-, Halogeno- und Pseudohalogeno-Liganden

Preparation, Redox Properties, and Structures of Mononuclear ?Simple”? Mono-, and Dinitrosyl Complexes of Molybdenum with Hydroxylamido(?1), Oximato, Halogeno, and Pseudohalogeno Ligands The compounds [(C₆H₅)₄P]₂[Mo(NO)(H₂NO)(NCS)₄] 1 , [(C₆H₅)₄P]₂ [Mo(NO)((C₂H₅)₂-CNO)(NCS)₄] 2 , [(C₆H₅)₄P]₂[Mo(NO)₂(NCS)₄] · CH₃OH, 3 [(C₆H₅)₄P]₃[Mo(NO)(CN)₅] · 2H₂O 4 , Cs₂[Mo(NO)Cl₄(H₂O)] 5 and Cs₂[Mo(NO)Cl₅] 6 were prepared and characterized by complete X-ray structure analysis. All complexes have a nearly linear MoNO moiety, whereas in the anions of 1 and 2 a pentagonal-bipyramidal, in 3 — 6 an octahedral coordination sphere of Mo is present. Complexes with {MoNO}ⁿ configuration (n = 4, 5, 6) can be converted into each other by remarkable redox-reactions. Some novel reactions of the hydroxylamido(?1)-ligand (formation of 2 and 3 ) are discussed very shortly.     

Charakterisierung von Distorsionsisomeren der Anionen Pentacyano-oxo-molybdat(IV) sowie Tetracyano-oxo-aqua-molybdat(IV) im festen Zustand. Kristallstrukturen von [(C6H5)4P]3[MoO(CN)5] · 7 H2O(grün), [(C6H5)4As]2 [MoO(OH2)(CN)4] · 4 H2O (blau) und [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (grün)

Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O (green), [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue), and [(C₆H₅)₄P]₂[MoO(OH₂) (CN)₄] · 4 H₂O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs₂H[MoO(CN)₅] (blue), [(CH₃)₄N]₂H[MoO(CN)₅] · 2 H₂O (blue) and [Cr(en)₃] [MoO(CN)₅] · 4 H₂O (green). The green [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN^? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN^? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm^?1 and 920 cm^?1, respectively. Blue and green salts containing the [MoO(OH₂)(CN)₄]^2? anion and [(C₆H₅)₄P]⁺ or [(C₆H₅)₄As]⁺ cations have been prepared and characterized by single crystal crystallography. [(C₆H₅)₄P]₂[MoO(OH₂)(CN)₄] · 4 H₂O (green) and [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue) crystallize monoclinic in the space group C—P2₁/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm^?1 and 980 cm^?1.     

Reaction of the Pincer‐type Ligand {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}— with [Ph3C]+[PF6]—. Unprecedented Rearrangement and Carbon‐Carbon Bond Formation

The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu‐C₆H₂}Li ( 1 ‐Li) with [Ph₃C]⁺[PF₆]^— gave the substituted biphenyl derivative 4‐[(C₆H₅)₂CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)₂]₂‐1, 1′‐biphenyl ( 5 ) which was characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu]C₆H₂}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)₂]₂C₆H₃ ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.     

Two novel diorganotin phosphonic diamides: syntheses,crystal structures,spectral properties and in vitro antibacterial studies

Two diorganotin complexes with general formulae SnCl₂(CH₃)₂[C₆H₅P(O)(NHCH(CH₃)₂)₂]₂ ( 1 ) and SnCl₂(CH₃)₂[C₆H₅P(O) (NHC(CH₃)₃)₂] ( 2 ) were prepared by the addition of one equivalent SnCl₂Me₂ to two equivalents of PhP(O)(NHⁱPr)₂ and PhP(O)(NH^tBu)₂, respectively. The compounds were characterized by elemental analysis, IR and multinuclear NMR (¹H, ¹³C, ³¹P and ¹¹⁹Sn) spectroscopy. The crystal structures of the complexes were determined by X‐ray single crystal analysis, which revealed that complex 1 has a distorted octahedral geometry and complex 2 has a distorted trigonal bipyramidal structure with non‐equivalent chlorine atoms. Preliminary antibacterial tests of the compounds against Gram‐positive and ‐negative bacteria were carried out using the filter paper disk method and chloroamphenicol was used as standard for comparison. Copyright © 2010 John Wiley & Sons, Ltd.     

Basische Metalle. XIII. Ein neuer Syntheseweg für Cyclopentadienyl-Rhodium-Phosphonat- aus Cyclopentadienyl-Rhodium-Phosphit-Komplexen

Basic Metals. XIII. A New Synthesis of Cyclopentadienylrhodium Phosphonate from Cyclopentadienylrhodium Phosphite Complexes C₅H₅Rh[P(OCH₃)₃]₂ reacts with alkali metal iodides MI (M = Li, Na, K) in two stages via the intermediate C₅H₅RhCH₃[P(O)(OCH₃) ₂]P(OCH₃)₃ to the corresponding bisphosphonate complexes C₅H₅RhCH₃[P(O)(OCH₃) ₂]₂M. Their properties suggest that they exist as contact ionpairs rather than dissociated ions. The reaction of C₅H₅RhCH₃[P(O)(OCH₃)₂]₂ Na with HCl in benzene yields the complex C₅H₅RhCH₃[P(O)(OCH₃) ₂]₂H, in which a chelate ligand with a P? O? H? O? P bridge is probably present. The acidic character of the bridging H atom is shown in the reaction with (CH₃)₃PCH₂ which leads to [C₅H₅RhCH₃{P(O)(OCH₃) ₂}₂][P(CH₃)₄]. C₅H₅RhCH₃[P(O)(OCH₃) ₂]₂Tl was formed in the reaction of C₅H₅RhCH₃[P(O)(OCH₃)₂]₂ H and thallium acetylacetonate. The n.m.r. spectra of the new phosphonate complexes are discussed.     

Übergangsmetall-carben-Komplexe. LXXX. α-Alkoxy- und α,α-dialkoxysubstituierte Phenylacetyl-(pentacarbonyl)metallate und Pentacarbonyl[alkoxy(benzyl)-carben]-Komplexe des Chroms und Wolframs

Vibrational Spectra of Dichlorophosphorylmethylamine CH₃? NH? P(?O)Cl₂ and its Adducts with SbCl₅ and SnCl₄ The vibrational spectra of liquid samples and solutions, as well as cryoscopic molecular weight determinations show that CH₃? NH? P(?O)Cl₂ exists largely in the dimeric form. The association occurs through hydrogen bridges. The adducts SbCl₅ · CH₃? NH? P(?O)Cl₂ and SnCl₄ · 2 CH₃? NH? P(?O)Cl₂ are formed through addition via an oxygen atom. The ligands have cis-configuration in the tin compound.     

Stannylene complexes of manganese,iron, and platinum

A number of stannylene complexes with different M: Sn ratios were obtained using various metals and substituents at the tin atom. The structures of the complexes were examined. A reaction of CpMn(CO)₂THF with (Ph₄As)⁺(SnCl₃)^? gave the ionic complex [Ph₄As]⁺[CpMn(CO)₂SnCl₃]^? (I). The action of C₆F₅MgBr on the complex C₅H₅Mn(CO)(NO)SnCl₃ produced C₅H₅Mn(CO)(NO)Sn(C₆F₅)₃ (II). Replacement of the Cl ions in the complex [CpFe(CO)₂]₂SnCl₂ by phenylacetylenide groups gave rise to the neutral complex [CpFe(CO)₂]₂Sn(C≡CPh)₂ (III). A reaction of (Dppm)PtCl₂ (Dppm is 1,1-bis(diphenylphosphino)methane) with SnCl₂ · 2H₂O in the presence of diglyme yielded the ionic complex [η³-CH₃O(CH₂)₂O(CH₂)₂OCH₃)SnCl]⁺[(η ²-Dppm)Pt(SnCl₃)₃]^? (IV). Transmetalation in a reaction of [(Dppe)₂CoCl][SnCl₃] · PhBr (Dppe is 1,2-bis(diphenylphosphino)ethane) with (Dcpd)PtCl₂ (Dcpd is dicyclopentadiene) in the presence of SnCl₂ afforded the ionic complex [Pt(Dppe)₂]₃[Pt(SnCl₃)₅]₂ (V). Structures I–V were identified by X-ray diffraction. In these structures, the formally single bonds between the atoms of transition metals M (Mn, Fe, and Pt) and Main Group heavy elements (Sn and P) having vacant d orbitals are appreciably shortened. The M-Sn bond length in complexes II and III are virtually independent of the substituents at the tin atom and the Pt-Sn bond length in complexes IV and V is virtually independent of the Pt: Sn ratio.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18‐Krone‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN

Crystal Structures of the Hexachlorometalates NH₄[SbCl₆], NH₄[WCl₆], [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ and (PPh₄)₂[WCl₆]·4CH₃CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH₄[SbCl₆] and NH₄[WCl₆] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH₄⁺ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl₆]^— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl₃ face each. In trans‐position to it the chlorine atom of a CH₂Cl₂ molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh₄)₂[WCl₆]·4CH₃CN crystallizes in the monoclinic space group P2₁/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl₆]^2— ion via weak C—H···Cl contacts.     

Solvent effect in the polymerization of e-caprolactone initiated with diethylaluminum ethoxide

Kinetics of ϵ-caprolactone (ϵCL) polymerization initiated with diethylaluminum ethoxide in benzene (C₆H₆) and acetonitrile (CH₃CN) as solvents was studied and compared with the previously studied polymerization conducted in tetrahydrofuran (THF) solvent. Kinetic data were analyzed in terms of the kinetic scheme: “propagation with aggregation,” assuming that actually propagating active species (P_n*) aggregate reversibly into the unreactive (dormant) species . The determined equilibrium constants of deaggregation (K_da) decrease with decreasing solvent polarity, namely K_da (in mol²·L⁻²) = (1.3 ± 0.7)·10⁻² (CH₃CN), (1.8 ± 0.5)·10⁻⁵ (THF), (4.1 ± 0.7)·10⁻⁶(C₆H₆), whereas for the rate constants of propagation the opposite is true, k_p (in mol⁻¹·L·s⁻¹) = (7.5 ± 0.3)·10⁻³ (CH₃CN), (3.87 ± 0.01)·10⁻² (THF), (8.6 ± 0.9)·10⁻² (C₆H₆) (25°C). The latter effect is explained by a specific solvation (the stronger the higher solvent polarity) of the active species already in the ground state in the elementary reaction of the poly(ϵCL) chain growth: C₂H₅[OC(O)(CH₂)₅]_nO(SINGLE BOND)Al(C₂H₅)₂ + ϵCL → C₂H₅[OC(O)(CH₂)₅]_n+1O(SINGLE BOND)Al(C₂H₅)₂. © 1996 John Wiley & Sons, Inc.     

Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

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.     

Organische Phosphorverbindungen XXIV Darstellung und Struktur von ketten- und ringförmigen Polyphosphinen

The new triphosphine CH₃P[P(C₆H₅)₂]₂, m. p. 130–134º, has been prepared in high yield by the interaction of (C₆H₅)₂PH and CH₃P[N(CH₃)₂]₂. This triphosphine is cleaved by CH₃J and Br₂. With sulfur it yields an adduct of the probable structure CH₃P[P(S)(C₆H₅)₂]₂, m. p. 163,5–166º.     

Formation of supramolecular complexes in reactions of adduct formation of zinc diethyldithiocarbamate with morpholine. Molecular structures and thermal properties

A supramolecular compound of the general formula [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₄ · NH(CH₂)₄O · C₂H₄{N(CH₂)₄O}₂ (I) was obtained and examined by X-ray diffraction analysis and thermography. According to X-ray diffraction data, the crystal lattice of compound I shows an unusual alternation of two independent centrosymmetric supramolecular complexes [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₂ · C₂H₄{N(CH₂)₄O}₂ (Ia) and [Zn{NH(CH₂)₄O} {S₂CN(C₂H₅)₂}₂]₂ · NH(CH₂)₄O (Ib). Either complex includes two molecules of an adduct of bis(diethyldithiocarbamato)zinc with morpholine and outer-sphere molecules of 1,2-dimorpholinoethane or morpholine. Adduct molecules are structurally nonequivalent in pairs and linked with solvate molecules by hydrogen bonds. The calculated geometries of the zinc polyhedra are intermediate between trigonal bipyramid and tetragonal pyramid. Thermal decomposition of supramolecular compound I proceeds through desorption of the outer-sphere and coordinated organic molecules; in the final step, defragmentation of the dithiocarbamate part gives zinc sulfide.