Chemistry of silicon-nitrogen compounds. 165. On the crystalline products from the reaction of silicon tetrachloride with nitrogen in a glow discharge. Single crystal X-ray structure determination of N(SiCl3)3 and Cl3SiN(SiCl2)2NSiCl3

Of the two crystalline products obtained by reacting a silicon tetrachloride/nitrogen mixture in a glow discharge tube, the more volatile (m. p. 78°C) has been confirmed to be tris(trichlorosilyl)amine NSi₃Cl₉ whereas the less volatile component (m. p. 66°C) has been identified as N,N′-bis(trichlorosilyl)-Si,Si′-tetrachloro-cyclodisildiazane N₂Si₄Cl₁₀. These conclusions are supported by mass and vibrational spectroscopy and single crystal X-ray structures. NSi₃Cl₉ possesses a nearly planar NSi₃ skeleton with average N? Si distances of 1.734(2) Å. The N₂Si₄ fragment of N₂Si₄Cl₁₀ is roughly planar with endocyclic N? Si? N and Si? N? Si angles of 89.2(1) and 90.8(1)°, respectively, and mean N? Si distances of 1.731(3) (endocyclic) and 1.687(3) Å (exocyclic).     

A structural study of Si6‐ring‐containing [Si6Cl14]2− chlorosilicates

The crystal structures of four substituted‐ammonium dichloride dodecachlorohexasilanes are presented. Each is crystallized with a different cation and one of the structures contains a benzene solvent molecule: bis(tetraethylammonium) dichloride dodecachlorohexasilane, 2C₈H₂₀N⁺·2Cl⁻·Cl₁₂Si₆, (I), tetrabutylammonium tributylmethylammonium dichloride dodecachlorohexasilane, C₁₆H₃₆N⁺·C₁₃H₃₀N⁺·2Cl⁻·Cl₁₂Si₆, (II), bis(tetrabutylammonium) dichloride dodecachlorohexasilane benzene disolvate, 2C₁₆H₃₆N⁺·2Cl⁻·Cl₁₂Si₆·2C₆H₆, (III), and bis(benzyltriphenylphosphonium) dichloride dodecachlorohexasilane, 2C₂₅H₂₂P⁺·2Cl⁻·Cl₁₂Si₆, (IV). In all four structures, the dodecachlorohexasilane ring is located on a crystallographic centre of inversion. The geometry of the dichloride dodecachlorohexasilanes in the different structures is almost the same, irrespective of the cocrystallized cation and solvent. However, the crystal structure of the parent dodecachlorohexasilane molecule shows that this molecule adopts a chair conformation. In (IV), the P atom and the benzyl group of the cation are disordered over two sites, with a site‐occupation factor of 0.560 (5) for the major‐occupied site.     

Zintl‐Anionen des Siliciums in den Halogeniden La3Cl2Si3 und La6Br3Si7

Zintl Anions of Silicon in the Halides La₃Cl₂Si₃ and La₆Br₃Si₇ La₃Cl₂Si₃ and La₆Br₃Si₇ are prepared at temperatures of around 950 °C from LaX₃ (X = Cl, Br), La metal and Si as starting materials. La₃Cl₂Si₃ crystallizes in C2/m with a = 1802(3), b = 420.6(4), c = 1058(2) pm, β = 97.9(2)°, and La₆Br₃Si₇ in Pmmn mit a = 1686.9(2), b = 412.93(11), c = 1185.2(1) pm. In both compounds the Si atoms are located in trigonal prisms of La atoms, which are connected through common triangular and rectangular faces to form layers. The bromine atoms connect the metal atom double layers. In La₃Cl₂Si₃ the Si atoms form zig‐zag chains, in La₆Br₃Si₇ chains build up from ‐connected Si₁₂ rings. Both compounds are metallic conductors.     

Tetrameric indium trichloride,a new modification of a widely used compound

The title compound, hexa‐μ‐chloro‐1:2κ⁴Cl;2:3κ⁴Cl;3:4κ⁴Cl‐hexachloro‐1κ²Cl,2κCl,3κCl,4κ²Cl‐hexakis­(diethyl­amine)‐1κ²N,2κN,3κN,4κ²N‐tetraindium(III), [(InCl₃)₄(Et₂NH)₆] or [In₄Cl₁₂(C₄H₁₁N)₆], lies about an inversion centre and consists of four octahedrally coordinated In centres linked by bridging Cl atoms to form three four‐membered In₂Cl₂ rings.     

Ba1.63La7.39Si11N23Cl0.42:Ce3+ – A Nitridosilicate Chloride with a Zeolite‐Like Structure

The nitridosilicate chloride Ba_1.63La_7.39Si₁₁N₂₃Cl_0.42:Ce³⁺ was synthesized by metathesis reaction starting from LaCl₃, BaH₂, CeF₃ and the product of the ammonolysis of Si₂Cl₆. The title compound is stable towards air and moisture. Diffraction data of a microcrystal were recorded using microfocused synchrotron radiation. X‐ray spectroscopy confirms the chemical composition of the crystal. IR spectra corroborate absence of N–H bonds. The compound is homeotypic to Ba₂Nd₇Si₁₁N₂₃ and crystallizes in space group Cmmm with a = 11.009(3), b = 23.243(8), c = 9.706(4) Å and Z = 4, R₁(all) = 0.0174. According to bond valence sum calculations, some crystallographic positions show complete occupancy by Ba or La whereas others contain significant amounts of both elements. In contrast to the structure prototype Ba₂Nd₇Si₁₁N₂₃, Ba_1.63La_7.39Si₁₁N₂₃Cl_0.42:Ce³⁺ contains chloride ions in channels of the SiN₄ tetrahedra network, hinting at various substitution possibilities of the complex zeolite‐like structure.     

Solid‐State NMR Investigations on the Amorphous Network of Precursor‐Derived Si2B2N5C4 Ceramics

Employing a multitude of modern solid state NMR techniques including ¹³C{¹⁵N}REDOR NMR, ¹H–¹³C CP NMR, ¹¹B MQMAS NMR spectroscopic experiments, the structural organization of Si₂B₂N₅C₄ ceramic has been studied. The experiments were executed on double isotope enriched (¹³C, ¹⁵N) and natural isotope abundance Si₂B₂N₅C₄ ceramics. The materials were synthesized by aminolysis and subsequent pyrolysis of intermediate pre‐ceramic polymers that were obtained from the single source precursor TSDE, 1‐(trichlorosilyl)‐1‐(dichloroboryl)ethane (Cl₃Si–CH(CH₃)–BCl₂). The result of the ¹³C{¹⁵N} REDOR NMR spectroscopic experiment shows that carbon atoms are incorporated into the network by bridging to nitrogen, which already occurs during the polymerization step. Furthermore, the combined results of ¹¹B NMR and ¹¹B MQMAS NMR indicate that boron atoms may also be connected to carbon in addition to nitrogen.     

Reactions of bis(trimethylsilyl)amine and -amide with MoOCl4

Oxo-Mo(VI) imido-chloride, [MoOCl₂(NH)(Et ₂O)] _n and nitrido-chloride, [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n have been synthesized by equimolar reactions of MoOCl₄ with HN(SiMe ₃)₂ and LiN(SiMe ₃)₂, respectively. Higher molar reactions of HN(SiMe ₃)₂ lead to imido-silylamido derivatives, [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , whereas those of LiN(SiMe ₃)₂ give silylimido bridged compounds, Mo₄O₄Cl₄(NSiMe ₃)₆ and Mo₄O₄(NSiMe ₃)₈. Elemental analyses, redox titration, magnetic moment, molecular weight, molar conductance, infrared,¹H-NMR and TG-DTG-DTA studies are reported.

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Reaktionen von Bis(trimethylsilyl)amin und -amid mit MoOCl₄

Zusammenfassung Durch equimolare Reaktionen von MoOCl₄ mit HN(SiMe ₃)₂ und LiN(SiMe ₃)₂ wurden die Oxo-Mo(VI) Imido-chloride [MoOCl₂(NH)(Et ₂O)] _n und die Nitrido-chloride [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n dargestellt. Höhermolekulare Reaktionen von HN(SiMe ₃)₂ führen zu Imido-silylamido Derivaten [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , währenddessen die von LiN(SiMe ₃)₂ silylimidoüberbrückte Verbindungen ergeben: Mo₄O₄Cl₄(NSiMe ₃)₆ und Mo₄O₄(NSiMe ₃)₈. Die Strukturen sind mit Elementaranalysen, Redoxtitrationen, Messung der magnetischen Momente, Molekulargewichten, molarer Leitfähigkeit, Infrarot,¹H-NMR und TG-DTG-DTA-Untersuchungen charakterisiert.

     

Bildung siliciumorganischer Verbindungen. 111. Die Hydrierung Si-chlorierter,C-spiroverbrückter 2,4-Disilacyclobutane mit LiAlH4 und iBu2AlH. Der Zugang zum Si8C3H20

Formation of Organosilicon Compounds. 111. The Hydrogenation of Si-chlorinated, C-spiro-linked 2,4-Disilacyclobutanes with LiAlH₄ or iBu₂AlH. The Access to Si₈C₃H₂₀ The hydrogenation of Si-chlorinated, C-spiro-linked 2,4-disilacyclobutanes containing C(SiCl₃)₂ terminal groups with LiAlH₄ in Et₂O proceeds under complete cleavage of the fourmembered rings and under elimination of one SiH₃ group. Such, Si₈C₃Cl₂₀ 4 forms (H₃Si)₂CH? SiH₂? CH(SiH₃)? SiH₂? CH(SiH₃)₂ 4 α, and even Si₈C₃H₂₀ 4a with LiAlH₄ forms 4 α. The hydrogenation of related compounds containing however CH(SiCl₃) terminal groups similarly proceeds under ring cleavage but no SiH₃ groups are eliminated. Such, (Cl₃Si)CH(SiCl₂)₂CH(SiCl₃) 41 forms (H₃Si)₂CH? SiH₂? CH₂(SiH₃) 41 α. However, in reactions with iBu₂AlH in pentane neither the disilacyclobutane rings are cleaved nor are SiH₃ groups eliminated. Only by this method Si₈C₃H₂₀ is accessible from 4 , Si₆C₂H₁₆ 3a from Si₆C₂Cl₁₆ 3 and Si₄C₂H₁₂ 41a from 41 . C(SiCl₃)₄ cleanly produces C(SiH₃)₄. Based on the knowledge about the different properties of LiAlH₄ and iBu₂AlH in hydrogenation reactions of disilacyclo-butanes it was possible to elucidate the composition and the structures of the hydrogenated derivatives of the product mixture from the reaction of MeCl₂Si? CCl₂? SiCl₃ with Si(Cu) [1] and to trace them back to the initially formed Si chlorinated disilacyclobutanes Si₆C₂Cl₁₅Me 34 , Si₆C₂Cl₁₄Me₂ 35 , Si₈C₃Cl₁₉Me 36 and Si₈C₃Cl₁₈Me₂ 37 . Compound 4a forms colourless crystals of space group P1 with a = 799.7(6), b = 1263.6(12), c = 1758.7(14) pm, α = 103.33(7)°, β = 95.28(6)°, γ = 105.57(7)° and Z = 4.     

Bildung siliciumorganischer Verbindungen. 110. Reaktionen von (Cl3Si)2CCl2, seiner Si-methylierten Derivate,von (Cl3Si)2CHCl, (Cl3Si)2C(Cl)Me und Me2CCl2 mit Silicium (Cu-Kat.)

Formation of Organosilicon Compounds. 110. Reactions of (Cl₃Si)₂CCl₂ and its Si-methylated Derivatives as well as of (Cl₃Si)₂CHCl, (Cl₃Si)₂C(Cl)Me and Me₂CCl₂ with Silicon (Cu cat.) The reactions of (Cl₃Si)₂CCl₂ 1 , its Si-methylated derivatives (Me₃Si)₂CCl₂ 8 , Me₃Si? CCl₂? SiMe₂Cl 9 , (ClMe₂Si)₂CCl₂ 10 , Me₃Si? CCl₂? SiMeCl₂ 11 , Cl₂MeSi? CCl₂? SiCl₃ 12 as well as of (Cl₃Si)₂CHCl 38 , (Cl₃Si)₂CClMe 39 and of Me₂CCl₂ with Si (Cu cat.) in a fluid bed reactor ( 38 and 39 also in a stirred solid bedreactor) arc presented. While (Cl₃Si)₂CCl₂ 1 yields C(SiCl₃)₄ 2 the 1,1,3,3-tetrachloro-2,2,4,4-tetrakis(trichlorsilyl)-1,3-disilacyclobutane Si₆C₂Cl₁₆ 3 and the related C-spiro linked disilacyclobutanes Si₈C₃Cl₂₀ 4 , Si₁₀C₄Cl₂₄ 5 , Si₁₂C₅Cl₂₈ 6 , Si₁₄C₆Cl₃₂ 7 this type of compounds is not obtained starting from the Si-methylated derivatives 8, 9, 10, 11 They Produce a number of variously Si-chlorinated and -methylated tetrasila- and trisilamethanes. However, Cl₂MeSi? CCl₂? SiCl₃ 12 forms besides of Si-chlorinated trisilamethanes also the disilacyclobutanes Si₆C₂Cl₁₅Me 34 and cis- and trans Si₆C₂Cl₁₄Me₂ 35 as well as the spiro-linked disilacyclobutanes Si₈C₃Cl₁₉Me 36 , Si₈C₃Cl₁₈Me₂ 37 . (Cl₃Si)₂CHCl 38 mainly yields HC(SiCl₃)₃ 31 and also the disilacyclobutanes cis- and trans-(Cl₃Si)HC(SiCl₂)₂CH(SiCl₃) 41 and (Cl₃Si)₂C(SiCl₂)₂CH(SiCl₃) 45 the 1,3,5-trisilacyclohexane [Cl₃Si(H)C? SiCl₂]₃ 44 as well as [(Cl₃Si)₂CH]₂SiCl₂, and (Cl₃Si)₂CClMe 39 mainly yields (Cl₃Si)₂C?CH₂and (Cl₃Si)₂besides of HC(SiCl₃)₃, MeC(SiCl₃)₃and (Cl₃Si)₃C? SiCl₂Me.,. Me₂CCl₂ 59 mainly yields Me(Cl)C?CH₂, Me₂CHCl and HCl₂Si? CMe₂? SiCl₃, besides of Me₂C(SiCl₃)₂ and Me₂C(SiCl₂H)₂ Compound 3 crystallizes triclinically in the space group P1 (Nr. 2) mit a = 900,3, b = 914,0, c = 855,3 pm, α = 116,45°, β = 101,44°, γ = 95,86° and one molecule per unit cell. Compound 4 crystallizes monoclinically in thc space group C2/c (no. 15) with a = 3158.3,b = I 103.7, c = 2037.4 pm, β = 1 16.62° and 8 molecules pcr unit cell. The disilacyclobutane ring of compound 3 is plane, showing a mean distance of d (Si-C) =19 1.8 pm and the usual deformations of endocyclic angles: α_Si = 94,2°> 85,8° = α_C.The spiro-linked disilacyclobutane rings of compound 4 are slightly folded by a mean angle of (19.0°). Their mean distances were found to be d (Si? C) = 190.4 pm relating to the central carbon atom and 192.0 pm to the outer ones, respectively. The deformations of endocyclic angles: α_Si = 93,9°> 84,4° = α_C are comparable to those of compound 3.     

Hydrogen‐bonded chains in 2,2,2‐trichloro‐N,N′‐bis(4‐methoxyphenyl)ethane‐1,1‐diamine and a three‐dimensional hydrogen‐bonded framework in 2,2,2‐trichloro‐N,N′‐bis(4‐chlorophenyl)ethane‐1,1‐diamine

In 2,2,2‐trichloro‐N,N′‐bis(4‐methoxyphenyl)ethane‐1,1‐diamine, C₁₆H₁₇Cl₃N₂O₂, molecules are linked into helical chains by N—H...O hydrogen bonds. Molecules of 2,2,2‐trichloro‐N,N′‐bis(4‐chlorophenyl)ethane‐1,1‐diamine, C₁₄H₁₁Cl₅N₂, are connected into a three‐dimensional framework by two independent Cl...Cl interactions and one C—H...Cl hydrogen bond.     

Neue anorganische Ringsysteme. XXIII. Hetero-Spirosilazane mit Germanium,Zinn und Zirkonium als spiralem Zentrum

Novel Inorganic Ring Systems. XXIII. Hetero Spirosilazanes with Ge, Sn, and Zr in the Spiral Center Symmetrical SiN-spiro[4,4]-nonanes of the skeleton composition Si₅N₄, Si₄N₄Ge, Si₄N₄Sn and Si₄N₄Zr and with the hetero atoms in the spiral center could be prepared for the first time in shape of their permethylated derivatives A 1 to E 1 via equations (1/2) as well as (3/4/5/6) respectively. They were confirmed in their structure by elemental analysis, proton n.m.r., mass, i.r., and Raman spectra.     

μ‐Aqua‐penta­aqua­[μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine]­chloro­dinickel(II) trichloride trihydrate

The title compound, μ‐aqua‐1:2κ²O‐penta­aqua‐1κ²O,2κ³O‐μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine‐1κ²N¹,N⁶:2κ²N²,N³‐chloro‐1κCl‐dinickel(II) trichloride trihydrate, [Ni₂Cl(C₁₆H₁₄­N₄)(H₂O)₆]Cl₃·3H₂O, consists of two Ni^II atoms, a 3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six‐membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) Å. The crystal structure is stabilized by an intra‐ and intermolecular hydrogen‐bonding scheme involving water–water and water–chlorine interactions.     

Die Clusterazide M2[Nb6Cl12(N3)6]·(H2O)4—x (M = Ca,Sr, Ba)

The Cluster Azides M₂[Nb₆Cl₁₂(N₃)₆]·(H₂O)_4—x (M = Ca, Sr, Ba) The isotypic cluster compounds M₂[Nb₆Cl₁₂(N₃)₆] · (H₂O)_4—x (M = Ca (1) , M = Sr (2) and M = Ba (3) ) have been synthesized by the reaction of an aequeous solution of Nb₆Cl₁₄ with M(N₃)₂. 1 , 2 and 3 crystallize in the space group Fd3¯ (No. 227) with the lattice constants a = 1990.03(23), 2015.60(12) and 2043, 64(11) pm, respectively. All compounds contain isolated 16e— clusters whose terminal positions are all occupied by orientationally disordered azide ligands.     

Li4Ca3Si2N6 and Li4Sr3Si2N6 – Quaternary Lithium Nitridosilicates with Isolated [Si2N6]10– Ions

The isotypic nitridosilicates Li₄Ca₃Si₂N₆ and Li₄Sr₃Si₂N₆ were synthesized by reaction of strontium or calcium with Si(NH)₂ and additional excess of Li₃N in weld shut tantalum ampoules. The crystal structure, which has been solved by single‐crystal X‐ray diffraction (Li₄Sr₃Si₂N₆: C2/m, Z = 2, a = 6.1268(12), b = 9.6866(19), c = 6.2200(12) Å, β = 90.24(3)°, wR₂ = 0.0903) is made up from isolated [Si₂N₆]^10– ions and is isotypic to Li₄Sr₃Ge₂N₆. The bonding angels and distances within the edge‐sharing [Si₂N₆]^10– double‐tetrahedra are strongly dependent on the lewis acidity of the counterions. This finding is discussed in relation to the compounds Ca₅Si₂N₆ and Ba₅Si₂N₆, which also exhibit isolated [Si₂N₆]^10– ions.     

Molybdänhalogenidcluster mit zwei terminalen Alkoholatliganden: Synthese und Kristallstrukturen von (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] und (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3

Molybdenum(II) Halide Clusters with two Alcoholate Ligands: Syntheses and Crystal Structures of (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ . Reaction of Mo₆Cl₁₂ with two equivalents of sodium methoxide in the presence of 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] ( 1 ), which can be converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃ ( 2 ) by metathesis with 9-Anthracenemethanole in propylene carbonate. As confirmed by X-ray single crystal structure determination ( 1 : C2/m, a=25.513(8) Å, b=13.001(3) Å, c=10.128(3) Å, β=100.204(12)°; : C2/c, a=15.580(5) Å, b=22.337(5) Å, c=27.143(8) Å, β=98.756(10)°) the compounds contain anionic cluster units [Mo₆ClCl(OR^a)₂]^2? with two alcoholate ligands in terminal trans positions ( 1 : d(Mo—Mo) 2.597(2) Å to 2.610(2) Å, d(Mo—Clⁱ) 2.471(3) Å to 2.493(4) Å, d(Mo—Cl^a) 2.417(8) Å and 2.427(8) Å, d(Mo—O) 2.006(13) Å; 2 : d(Mo—Mo) 2.599(3) Å to 2.628(3), d(Mo—Clⁱ) 2.468(8) Å to 2.506(7) Å, d(Mo—Cl^a) 2.444(8) Å and 2.445(7) Å, d(Mo—O) 2.012(19) Å).     

4,4,6,6‐Tetra­chloro‐2,2‐(propyl­ene­dioxy­di‐o‐phenyl­enedi­imino)‐2λ5,4λ5,6λ5‐cyclotriphosphazene

The title compound, C₁₅H₁₆Cl₄N₅O₂P₃, is a cyclo­phosphazenic lariat (PNP‐pivot) ether with a spiro‐cyclic 12‐membered macrocyclic ligand containing two ether O and two N atoms; the phosphazene ring is nearly planar. In the macrocyclic ring, there is a four‐center (trifurcate) N—H⋯O/N—H⋯N hydrogen bond. The relative inner‐hole size of the macrocycle is estimated as approximately 0.95 Å.     

Spectral and magnetic studies of polynuclear copper(II) complexes of Schiff base derived from ethylenediamine and ethylacetoacetate

Summary The Schiff base (L), prepared by the condensation of two molecules of ethyl acetoacetate and one molecule of ethylenediamine reacts with copper(II) chloride to give poiynuclear complexes of the type Cu₃L Cl₆, Cu₄L Cl₈, Cu₅L Cl₁₀, Cu₆L Cl₁₂, Cu₇L Cl₁₄ and Cu₈L Cl₁₆. Elemental analyses, molar conductivities, magnetic susceptibilities, x-ray powder diffraction and i.r. spectral studies have been used to characterize the complexes. The i.r. spectra show that the Schiff base binds in a tetradentate manner and the spectral and magnetic studies suggest the presence of a chlorine bridge between the copper atoms. The magnetic susceptibility of the complexes follows the Curie-Weiss law.     

1,1,3,3-Tetrachlordisilazan

1,1,3,3-Tetrachlorodisilazane The new compound 1 can be prepared by the reaction of calciumoctamminedichloride, CaCl₂(NH₃)₈, with trichlorosilane, HSiCl₃. IR, Raman, ¹H and ²⁹Si NMR spectra show a planar Si₂NH framework, probably C₂-symmetry of the whole molecule and a symmetrical distribution of the four chlorine atoms. In 1 we have got a compound with Bronsted and Lewis acidity, which reacts with three equivalents of pyridine to HSiCl₂(py)₂? NH(py)? HSiCl₂. This addition compound exhibits a fourfold and a sixfold coordinated silicon atom as is shown by a ²⁹Si-solid-NMR spectrum. By thermal decomposition of 1 the new compound 1,3,5-trichloro-2,4,6-tris(dichlorosilyl)-cyclo-1,3,5-trisil-2,4,6-triazane, Si₆Cl₉H₆N₃, 4 , is formed. With piperidine, 1 reacts by substitution of all four chlorine atoms to compound 5 , whereas with diazomethane the NH-functionality is converted to a NCH₃ group in 6 . Attempts of lithiation lead mainly to a substitution of the chlorine atoms by alkyl groups     

Phosphorus-nitrogen compounds: Reinvestigation of the reactions of hexachlorocyclotriphosphazene with 1,4-butane- and 1,6-hexane-diols—NMR studies of the products

Reactions of hexachlorocyclotriphosphazene N₃P₃Cl₆ (1) with 1,4-butane-(2) and 1,6-hexane-diols (3) in (1:1:2, 1:2:4, and 1:3:6) stoichiometries in THF solution at room temperature (r.t.) and under refluxing conditions yield a total of 15 products: two open chain, N₃P₃Cl₅[O(CH₂)_nOH] (n = 4, 6) (4, 5), two mono-spiro, N₃P₃Cl₄[O(CH₂)_nO] (n = 4, 6) (6, 7), two mono-ansa, N₃P₃Cl₄[O(CH₂)_nO] (n = 4,6) (8, 9), two dispiro, N₃P₃Cl₂[O(CH₂)_nO]₂ (n = 4, 6) (10, 11), two spiro-ansa, N₃P₃Cl₂[O(CH₂)_nO]₂ (n = 4, 6) (12, 13), one tri-spiro, N₃P₃[O(CH₂)₄O]₃ (14), two single-bridged, N₃P₃Cl₅[O(CH₂)_nO]N₃P₃Cl₅ (n = 4, 6) (15, 16), one double-bridged, N₃P₃Cl₄[O(CH₂)₆O]₂N₃P₃Cl₄ (17), and one tri-bridged, N₃P₃Cl₃[O(CH₂)₆O]₃N₃P₃Cl₃ (18) derivatives. Their structures have been elucidated by MS, ³¹P, and ¹H NMR spectroscopy. The results obtained, based on the synthesis, characterization, product types, and the relative yields, are compared with those of previous studies on the reactions of 1 with 1,2-ethane-, 1,3-propane-, 1,4-butane-, 1,5-pentane-, and 1,6-hexane-diols.     

Synthesis of Ethylene‐bridged Heterocyclic Bidentate P(III)N‐Ligands — Oxidation and Complexation Studies

A series of phosphor(III)inanone ligands 4‐7 , linked by ethylene bridges between the nitrogen atoms of the heterocyclic rings, were synthesized by the reaction of the bis‐PCl derivative 3 with the appropriate trimethylsilylamines. The bis‐phosphor(V)inanone compounds 8‐11 were obtained by the oxidation of 4‐7 with hexafluoroacetone (HFA). Oxidation of 4 and 6 with tetrachloro‐orthobenzoquinone (TOB) gave the bis‐phosphor(V)inanones 12 and 13 . The reaction of 4‐6 with [Pt(COD)Cl₂] led to the platinum complexes 14‐16 . All the σ³‐phosphorinanone compounds 4‐7 and the σ⁵‐phosphorinanone compounds 8‐10 , 12 and 13 exist as a mixture of two conformers, as indicated by two signals in the ³¹P‐NMR spectra. However, compounds 9 and 11 exist as single conformers, both display only one sharp singlet in the ³¹P‐NMR spectra. The Pt‐complexes 15 and 16 contain two conformers; one conformer of 16 could be isolated by crystallization. X‐ray crystal structure determinations for compounds 8 , 14 and 16 were conducted, revealing inversion symmetry for 8 and cis arrangement for 14 and 16 .