Manganese(III) acetate based oxidative cyclizations of 3-oxopropanenitriles with conjugated alkenes and synthesis of 4,5-dihydrofuran-3-carbonitriles containing heterocycles

4,5-Dihydrofuran-3-carbonitriles 3a-i were obtained through oxidative cyclizations of 3-oxo-3-phenylpropanenitrile 1a, 3-oxo-3-thien-2-ylpropanenitrile 1b, 3-(2-furyl)-3-oxopropanenitirle 1c, 3-(1-benzofuran-2-yl)-3-oxopropanenitrile 1d, and 4,4-dimethyl-3-oxopropanenitrile 1e mediated manganese(III) acetate with 1,1-diphenyl-1-butene 2a and 1,2-diphenyl-1-pentene 2b. The treatments of these 3-oxopropanenitriles with 2-thienyl substituted alkenes such as 2-[(E)-2-phenylvinyl]thiophene 2c, 2-[(E)-1-methyl-2-phenylvinyl]thiophene 2d, and 2-(1-phenylvinyl)thiophene 2e formed 5-(2-thienyl)-4,5-dihydrofuran-3-carbonitriles 3j-r in good yields (45-93%). As a result, 2-thienyl substituted alkenes formed products in higher yields than phenyl substituted derivatives.     

腐植酸作用下γ-六氯环己烷在冰相中的光转化

研究了腐植酸(HA)存在下冰相体系中γ-六氯环己烷(γ-HCH)的光转化规律. 结果表明, HA浓度对γ-HCH的光转化率呈现低浓度促进而高浓度抑制的现象; 盐离子浓度、 N\begin{array}{c}{O}_2^{-}\end{array}及N\begin{array}{c}{O}_3^{-}\end{array}对γ-HCH的光转化率均有促进作用; 低浓度Fe³⁺对γ-HCH的光转化率有促进作用, 当Fe³⁺的浓度增大到50 μmol/L时, 呈现抑制效应; γ-HCH在不同pH值条件下光转化速率的大小顺序为碱性>中性>酸性. 冰相中HA通过产生单线态氧(¹O₂)、 羟基自由基(·OH)及三重激发态(HA^*)加速γ-HCH的光转化. HA存在下γ-HCH的光转化产物主要是五氯环己烯、 邻二氯苯和对二氯苯、 一氯苯, 光转化过程中¹O₂通过消耗中间产物间接加速了γ-HCH的光转化过程.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [(Mo6X)Y]2–; Xi = Cl,Br; Ya = NO3, NO2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Mo₆X)Y]^2–; Xⁱ = Cl, Br; Y^a = NO₃, NO₂ By treatment of [(Mo₆X)Y]^2–; Xⁱ = Y^a = Cl, Br with AgNO₃ or AgNO₂ by strictly exclusion of oxygene in acetone the hexanitrato and hexanitrito cluster anions [(Mo₆X)Y]^2–, Y^a = NO₂, NO₃ are formed. X-ray structure determinations of (Ph₄As)₂[(Mo₆Cl)(NO₃)] · 2 Me₂CO ( 1 ) (monoclinic, space group P2₁/n, a = 12.696(3), b = 21.526(1), c = 14.275(5) Å, β = 115.02(2)°, Z = 2), (n-Bu₄N)₂[(Mo₆Br)(NO₃)] · 2 CH₂Cl₂ ( 2 ) (monoclinic, space group P2₁/n, a = 14.390(5), b = 11.216(5), c = 21.179(5)Å, β = 96.475(5)°, Z = 2) and (Ph₄P)₂[(Mo₆Cl)(NO₂)] (3) (monoclinic, space group P2₁/n, a = 11.823(5), b = 13.415(5), c = 19.286(5) Å, β = 105.090(5)°, Z = 2) reveal the coordination of the ligands via O atoms with (Mo–O) bond lengths of 2.11–2.13 Å, and (MoON) angles of 122–131°. The vibrational spectra of the nitrato compounds show the typical innerligand vibrations ν_as(NO₂) (∼ 1500), ν_s(NO₂) (∼ 1270) and ν(NO) (∼ 980 cm^–1). The stretching vibrations ν(N=O) at 1460–1490 cm^–1 and ν(N–O) in the range of 950–1000 cm^–1 are characteristic for nitrito ligands coordinated via O atoms.     

Formation of new 4-isocyanobut-2-enenitriles by thermal ring cleavage of 3-pyridyl azides

A new thermal ring cleavage of 3-pyridyl nitrenes for the formation of 4-isocyanobut-2-enenitrile products is reported. Thermolysis of 4-(thien-3-yl)-3-pyridyl azide 1 and 3-azido-4-(1-TIPS-1H-pyrrol-3-yl)pyridine 5 afforded two new isonitrile-nitrile products by ring cleavage; 4-isocyano-2-(thiophen-3-yl)but-2-enenitrile (3, 27%) and 4-isocyano-2-(1-TIPS-1H-pyrrol-3-yl)but-2-enenitrile (7, 20%), in addition to our previously reported pyrido[3,4-b]thienopyrrole (2, 29%) and pyrido[3,4-b]pyrrolo[3,2-d]pyrrole (6, 71%) products. Minor amounts of 2-(thien-3-yl)-1H-pyrrole-3-carbonitrile (4, 6%), formed by ring contraction, were also isolated after thermolysis of azide 1. Isonitriles 3 and 7 underwent degradation into amine 3b and formamide 7a by acidic hydrolysis. The nature and chemistry of compounds 3, 4 and 7 were investigated.     

Involvement of Singlet Oxygen in the Solid‐State Photochemistry of P3HT

We studied the role that singlet oxygen plays in the solid‐state photochemistry of poly(3‐hexylthiophene) (P3HT). The photosensitized formation of singlet oxygen by solid‐state P3HT and its subsequent reactivity on the polymer were investigated. Using a fluorescent probe, it was found that singlet oxygen (¹O₂) could be produced by irradiation of P3HT by photosensitization, with no oxidation of the polymer. In addition, ¹O₂ was directly formed on P3HT via a chemical reaction, again with no oxidation of the polymer. These results give strong evidence that ¹O₂ is not the principal photo‐oxidative degradation intermediate of P3HT, which conflicts with previous reports.

     

Syntheses of Heterocycles from the Sodium Salts of 3-(1-Adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-Adamantyl)-1-hydroxy-1-buten-3-one

The interaction of the sodium salts of 3-(1-adamantyl)-1-hydroxy-1-propen-3-one and 4-(1-adamantyl)-1-hydroxy-1-buten-3-one with hydroxylamine, hydrazine, and guanidine leads to the synthesis of 5-(1-adamantyl)-5-hydroxy- and 5-(1-adamantylmethyl)-5-hydroxy-2-isoxazolines, 3-(1-adamantyl)- and 3-(1-adamantylmethyl)pyrazoles, 3-(1-adamantyl)-2-phenylpyrazole, and 4-(1-adamantyl)-2-amino- and 4-(1-adamantylmethyl)-2-aminopyrimidines.     

Thermochemistry of the Ternary Complex Nd（Et2dtc）3（phen）

Introduction A series of lanthanide sulfide complexes have beenlargely used for ceramics and thin film materials1 andthese complexes could be prepared from the precursorswhich are the compounds containing lanthanide-sulfurbonds.2-4 For instance, the compounds synthesized with[(alkyl)2dtc]-, phen?H2O and lanthanide salts were usedas the volatile precursors for preparing lanthanide sul-fide, its friction properties in lubricant was investigatedin literature 5 and the preparation and propertie…     

Reactions of (E)-1,2-di(3-guaiazulenyl)ethylene and 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene with tetracyanoethylene (TCNE) in benzene: comparative studies on the products and their spectroscopic properties

Reactions of the title ethylene derivatives, (E)-1,2-di(3-guaiazulenyl)ethylene (1) and 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene (2), with a 2 M amount of TCNE in benzene at 25 °C for 24 h under argon give new cycloaddition compounds, 1,1,2,2,11,11,12,12-octacyano-3-(3-guaiazulenyl)-8-isopropyl-5,10-dimethyl-1,2,3,6,9,10a-hexahydro-6,9-ethanobenz[a]azulene (3) from 1 and 1,1,2,2,11,11,12,12-octacyano-8-isopropyl-3,3-bis(4-methoxyphenyl)-5,10-dimethyl-1,2,3,6,9,10a-hexahydro-6,9-ethanobenz[a]-azulene (4) from 2, respectively, in 66 and 87% isolated yields. Comparative studies on the above reactions as well as the spectroscopic properties of the unique products 3 and 4, possessing interesting molecular structures, are reported and, further, a plausible reaction pathway for the formation of these products is described.     

Stereospecific syntheses of sex pheromones of the californian red scale and white peach scale (Homoptera:Diaspididae) based on 1,4-cis-hydrogenation of dienes

Stereospecific syntheses of (±)-3-methyl-6-isopropenyl-3(Z),9-decadien-1-yl acetate and (±)-3,9-dimethyl-6-isopropenyl-3(Z),9-decadien-1-yl propionate (the Racemoc forms of the pheromones of the scalesAonidiella aurantii andPseudaulascaspis pentagona) with a geometrical purity of the (Z)-trisubstituted double bond not lower than 99 % were performed. The key step in both syntheses was the 1,4-cis-hydrogenation of the corresponding ethyl 3-methyl-6-(1, 1-ethylenedioxyethyl)-2,4,9-decatrienoates catalyzed with chromium carbonyl complexes. These 2,4-dienes were obtained in five conventional steps including the alkylation of ethyl acetoacetate by the appropriate 1-bromo-3-butenes and the Horner-Emmons olefination of the corresponding -branched aldehydes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2026–2031, October, 1995.     

Reaction of guaiazulene with o-formylbenzoic acid in diethyl ether (or methanol) in the presence of hexafluorophosphoric acid: comparative studies on H and C NMR spectral properties of 3-guaiazulenylmethylium- and 3-guaiazulenium-ion structures

Reaction of guaiazulene (1) with o-formylbenzoic acid (2) in diethyl ether in the presence of hexafluorophosphoric acid at 25 °C for 90 min gives the corresponding monocarbenium-ion compound, [2-(carboxy)phenyl](3-guaiazulenyl)methylium hexafluorophosphate (3), quantitatively, which upon treatment with aq NaHCO₃ leads to 3-(3-guaiazulenyl)-2-benzofuran-1(3H)-one (5) in 96% isolated yield. Similarly, reaction of 1 with 2 in methanol under the same conditions as the above reaction affords two kinds of inseparable monocarbenium-ion compounds, 3 and (3-guaiazulenyl)[2-(methoxycarbonyl)phenyl]methylium hexafluorophosphate (4) with an equilibrium between them, which upon reaction with a solution of NaBH₄ in ethanol at 25 °C for 30 min leads to 5 in 46% isolated yield and (3-guaiazulenyl)[2-(methoxycarbonyl)phenyl]methane (6) in 37% isolated yield. Along with the ¹H and ¹³C NMR spectral properties of a solution of 5 in trifluoroacetic acid-d₁ at 25 °C, whose molecular structure is converted to a ca. 1:1 equilibrium mixture of 7 possessing a partial structure of the 3-guaiazulenylmethylium-ion and 8 possessing a partial structure of the 3-guaiazulenium-ion, comparative studies on the ¹H and ¹³C NMR spectral properties of 7 and 8 with those of the monocarbenium-ion compound, (3-guaiazulenyl)[4-(methoxycarbonyl)phenyl]methylium hexafluorophosphate (A), 5, and 6 are reported. From these NMR studies, it can be inferred that the positive charge of the 3-guaiazulenylmethylium-ion part of 7 apparently is transferred to the seven-membered ring, generating a resonance form of the 3-guaiazulenylium-ion structure η′, and the same result can be inferred for the previously documented monocarbenium-ion compounds A-I. Moreover, referring to a comparative study on the C-C bond lengths of A observed by the X-ray crystallographic analysis with those of the optimized (3-guaiazulenyl)[4-(methoxycarbonyl)phenyl]methylium-ion structure for A calculated by a WinMOPAC (Ver. 3.0) program using PM3, AM1, or MNDOD as a semiempirical Hamiltonian, the optimized [2-(carboxy)phenyl](3-guaiazulenyl)methylium-ion structure for 3 calculated using PM3 is described.     

Synthesis of Gingerenone C and 5-Hydroxy-1-(4'-hydroxy- 3'-methoxyphenyl)-7-(4"-hydroxyphenyl)-3-heptanone

The two diarylheptanoids (E)-1-(4'-hydroxy-3'-methoxyphenyl)-7-(4"-hydroxyphenyl) hept-4-en-3-one 1 (Gingerenone C) and (±)-5-hydroxy-1-(4'-hydroxy-3'-methoxyphenyl)-7-(4"-hydroxyphenyl)-3-heptanone 2 were synthesized from vanillin 3 and 4-hydroxybenzaldehyde 9.     

Fischer Synthesis of 1-; 5-; and 7-Substituted 3-(N-Acylamino)-2-phenylindoles

Arylhydrazones were obtained by the reaction of arylhydrazines with -(N-acylamino)acetophenones and were converted into 3-(N-acylamino)-2-phenylindoles with substituents at positions 1, 5, 6, and 7 by Fischer cyclization.     

Efficient,Stereoselective Approach to the Synthesis of 3-(1-Phenyl-2-(Z-styrylsulfonyl)-1H-imidazol-4-yl)-2H-chromen-2-ones

Reaction of phenyl acetylene with 3-(1-aryl-2-mercapto-4-imidazolyl)-2H-1-benzopyran-2-ones (4) in the presence of sodium hydroxide in absolute ethanol led to the formation of 3-(1-phenyl-2-(Z-styrylthio)-1H-imidazol-4-yl)-2H-chromen-2-ones (6) in excellent yields. These, on further oxidation with H₂O₂/AcOH, gave the corresponding sulfones (7) with retention of stereochemistry.

2-芳胺基-5-[5′-氨基-1′-(4″-氯苯基)-1′,2′,3′-三唑-4′-基]-1,3,4-噻二唑的合成~≠

1-[5’-氨基-1’-(4”-氯苯基)-1,2,3-三唑-4’-甲酰基]-4-芳基-3-氨基硫脲在浓硫酸催化下环化得到2-芳胺基-5-[5’-氨基-1’-(4”-氯苯基)-1’,2’,3’,-三唑-4’-基]-1,3,4-噻二唑2a～i,依次法合成了九个标题化合物,收率为30～74％。化合物2i的结构用X-光衍射单晶分析确证。     

Synthesis of polyfunctionalized furans from 3-acetyl-1-aryl-2-pentene-1,4-diones

The BF₃-catalyzed cyclization of 3-acetyl-1-aryl-2-pentene-1,4-diones 1a-e in the presence of water in boiling tetrahydrofuran gave bis(3-acetyl-5-aryl-2-furyl)methanes 2a-e in 26-79% yields along with a small amount of 3-acetyl-5-aryl-2-methylfurans 3a-e. The exact structure of 2a was determined by X-ray crystallography. The use of a half volume of the solvent for the reaction of 1a resulted in the formation of 2,4-bis(3-acetyl-5-phenyl-2-furfuryl)-3-acetyl-5-phenylfuran (4) together with 2a and 3a. A similar reaction of 1a was carried out in the presence of 3-acetyl-5-(4-methylphenyl)-2-methylfuran (3d) to afford 4-(3-acetyl-5-phenyl-2-furfuryl)-3-acetyl-5-(4-methylphenyl)-2-methylfuran (5) in 49% yield. The BF₃-catalyzed reaction of 1a with 2,4-pentanedione in dry tetrahydrofuran at 23°C gave 3-(3-acetyl-5-phenyl-2-furfuryl)-4-hydroxy-3-penten-2-one (6a) and 3-(3-acetyl-2-methyl-4-phenyl-5-furyl)-4-hydroxy-3-penten-2-one (7a) in 66 and 24% yields, respectively. The product distribution depended on the reaction temperature. A similar reaction of 1b-e also yielded the corresponding trisubstituted furans 6b-e and tetrasubstituted furans 7b-e in good yields. These results suggested the presence of the furfuryl carbocation intermediate A during the reaction. The one-pot synthesis of 6a and 7a was also achieved by a similar reaction using phenylglyoxal. The deoxygenation of 1a with triphenylphosphine gave 3a in 88% yield, while 1a was treated with concentrated hydrochloric acid to yield 3-acetyl-2-chloromethyl-5-phenylfuran (8) which was quantitatively transformed in ethanol into 3-acetyl-2-ethoxymethyl-5-phenylfuran (9) and in water into 3-acetyl-5-phenylfurfuryl alcohol (10), respectively. In addition, the Diels-Alder reaction of cyclopantadiene with 1a gave the corresponding [4+2] cycloaddition products 11 and 12.     

Acyl- und Alkylidenphosphane. XXXIV [1]. Methoxycarbonylphosphane – Verbindungen aus dem Umfeld des Phosphaalkins PC?O?Li(dme)2

Acyl- and Alkylidenephosphanes. XXXIV. Methoxycarbonylphosphanes – Compounds closely related to the Phosphaalkyne P?C? O? Li(dme)₂ Whereas methyl fluoroformate reacts with an equimolar amount of bis(tetrahydrofuran)lithium bis(trimethylsilyl)phosphanide ( 1a )

1 Die Numerierung des betreffenden Lithiumphosphanids wird um das Suffix a erweitert, wenn von einer Röntgenstrukturanalyse her Gehalt an koordinierendem Solvens und Konstitution bekannt sind. Nach Möglichkeit beziehen wir uns dann im Text und in den Gleichungen auf derartige Spezies.

in 1,2-dimethoxyethane to give an inseparable mixture of tris(methoxycarbonyl)- ( 3 ) and tris(trimethylsilyl)phosphane, colourless crystals of lithium bis(methoxycarbonyl)phosphanide-1,2-dimethoxyethane (2/3) ( 4a ) are isolated in 84% yield from an analogous reaction with (1,2-dimethoxyethane- O,O ′)lithium phosphanide ( 2a ) in a molar ratio of 2:3. When, however, this ratio is changed to 1:2 or 1:1, the ³¹ P nmr spectra of those solutions show the formation of the by-product lithium methoxycarbonylphosphanide ( 10 ) or methoxycarbonylphosphane ( 6 ) respectively. The function of phosphanide 10 as an important intermediate in the synthesis of the phosphaalkyne P?C? O? Li(dme) ₂ ( Ia ) [1] is discussed in detail. With trifluoroacetic acid in 1,2-dimethoxyethane the diacylphosphanide 4a is converted via a lithium-hydrogen exchange into bis(methoxycarbonyl)phosphane ( 9 ). Unlike 1,3-diketones and other diacylphosphanes [25], solutions of this compound do not show the presence of an enol tautomer even in very unpolar solvents. Tris(methoxycarbonyl)phosphane ( 3 ) obtained in a pure state from methyl chloroformate and phosphanide 2a , might decarboxylate to give the corresponding bis(methoxycarbonyl)methyl derivative 5 when the reaction mixture is worked up. ³¹P and characteristic ³¹C nmr data of these methoxycarbonylphosphanes and their related lithium phosphanides are compared with each other, the tris(phenoxycarbonyl) ( 7 ) and the bis(methoxycarbonyl)phenyl compound 8 being included. An x-ray structure determination (P1 ; a 715.8(2); b = 899.5(1); c = 1262.7(2)pm; α = 99.93(1)°; β = 96.01(1)°; γ = 104.81(1)° at ?100±3°C; Z = 1 dimer; wR₂ = 0.152) shows lithium bis(methoxycarbonyl)phosphanide-1,2-dimethoxyethane (2/3) ( 4a ) to crystallize as a centrosymmetric neutral complex. Either lithium square pyramidally coordinated is bound to both carbonyl oxygen atoms of an almost planar bis(methoxy-carbonyl)phosphanide {Li? O_av. 197.4; O ‥ O 280.9} as well as of an 1,2-dimethoxyethane ligand (210.3; 261.6) and is brigded by another solvent molecule (204.0 pm). Further characteristic average bond lengths and angles are as follows: P$ \ddot - $C 179.5; C$ \ddot - $O 122.2; C? O 136.5; O? CH₃ 143.2 pm; C$ \ddot - $P$ \ddot - $C 98.8°; P$ \ddot - $C$ \ddot - $O 132.5°; P$ \ddot - $C? O 107.9°.     

二(2-乙基己基)二硫代次膦酸对硝酸溶液中Am3+和Eu3+的萃取

以正十二烷作稀释剂, 研究了二(2-乙基己基)二硫代次膦酸(D2EHDTPA)对HNO₃溶液中Am³⁺和Eu³⁺的萃取行为. 考察了酸度、 萃取剂及N{\mathrm{O}}_3^{-}浓度和皂化度对萃取的影响. 在考察的pH范围(2.5~4.5)内, D2EHDTPA萃取Am³⁺和Eu³⁺的分配比(D)随pH值增大而增加; pH=3.65时, 分离因子(SF_Am/Eu)值达到最大(4000). 随D2EHDTPA浓度的增加, D_Am和D_Eu值均增加. 斜率分析表明, D2EHDTPA萃取Am³⁺和Eu³⁺主要形成3:1和2:1型的萃合物. N{\mathrm{O}}_3^{-}未直接参与D2EHDTPA对Am³⁺和Eu³⁺的萃取反应. D2EHDTPA经NaOH皂化后, 萃取能力显著增强, SF_Am/Eu值提高到10⁴量级, 萃取容量约为理论值的60%. 此外, 使用高分辨质谱、 红外光谱和等温微量热滴定方法研究了D2EHDTPA与Eu³⁺的配位化学行为, 得到了金属离子与配体的组成比、 络合物稳定常数以及配位热力学参数ΔH, ΔS和ΔG值.     

Unexpected dimerization during hydrogenation of 2-(2-pyridylmethylene)-3(2H)-benzofuran-3-ones

Palladium catalyzed hydrogenation of 2-(2-pyridylmethylene)-3(2H)-benzofuran-3-ones (1-3) gave besides the expected 2,α-dihydro products 8-10 pentacyclic dimers formed by an attack of a semihydrogenated species on the substrate.     

New silatranes possessing urea functionality: Synthesis, characterization and their structural aspects

The present work aims at the synthesis of various novel silatranes bearing substituted urea functionality. Nucleophilic addition of various amines (morpholine, aniline, ethylenediamine and 3-aminopropyltriethoxysilane) to 3-isocyanatopropyltriethoxysilane resulted in the four triethoxysilanes; N-[3-(triethoxysilyl)propyl]morpholine-4-carboxylic acid amide (1), 1-[3-(triethoxysilyl)propyl]-3-phenylurea (2), 1,2-bis{N′-[3-(triethoxysilyl)propyl]ureido}-ethane (3) and N-[3-(triethoxysilyl)propyl]-N′-[3-(triethoxysilyl)propyl]urea (4), respectively. In the presence of a base the resulting silanes undergo transesterification reaction with triethanolamine, thus forming the corresponding silatranes, N-(3-silatranylpropyl)morpholine-4-carboxylic acid amide (5), 1-(3-silatranylpropyl)-3-phenylurea (6), 1,2-Bis[N′-(3-silatranylpropyl)ureido]-ethane (7) and N-(3-silatranylpropyl)-N′-(3-silatranylpropyl)urea (8), respectively. Among these are four novel compounds (5-8), which were characterized by elemental analysis, IR, multinuclear (¹H, ¹³C and ²⁹Si) NMR and mass spectroscopy. Structures of compounds 5 and 6 were deduced by X-ray crystallography. Single crystal X-ray studies revealed distorted trigonal bipyramidal coordination about Si in 5 and 6 with Si-N bond distance of 2.121(1) Å and 2.189(2) Å, respectively.     

Bis[N-(trimethylsilyl)iminobenzoyl]phosphanide des Lithiums und Zinks – Synthese sowie NMR-spektroskopische,strukturelle und quantenchemische Untersuchungen

Acyl- and Alkylidenephosphanes. XXXV. Bis[ N -(trimethylsilyl)iminobenzoyl]phosphanides of Lithium and Zinc – Syntheses as well as NMR Spectroscopic, Structural, and Quantumchemical Studies From the reaction of bis(tetrahydrofuran)lithium bis(trimethylsilyl)phosphanide with two equivalents of benzonitrile in 1,2-dimethoxyethane, the yellow dme complex ( 2 a ) of lithium bis[N-(trimethylsilyl)iminobenzoyl]phosphanide ( 2 ) was obtained in 69% yield. However, the intermediate {1-[N-lithium-N-(trimethylsilyl)amido]benzylidene}trimethylsilylphosphane ( 1 ), formed by an analogous 1 : 1 addition in diethyl ether, turned out to be unstable and as a consequence could be characterized by nmr spectroscopic methods only; attempts to isolate the compound failed, but small amounts of the neutral complex 2 b , with the ligands benzonitrile and tetrahydrofuran coordinated to lithium, precipitated. The reaction of compound 2 with zinc(II) chloride in diethyl ether gives the orange-red spiro-complex zinc bis{bis[N-(trimethylsilyl)iminobenzoyl]phosphanide} ( 3 ); this complex is also formed from bis[N-(trimethylsilyl)iminobenzoyl]phosphane ( 4 ), easily amenable by a lithium hydrogen exchange of 2 a with trifluoroacetic acid [18], and zinc bis[bis(trimethylsilyl)amide]. As derived from nmr spectroscopic studies and x-ray structure determinations, compounds 2 a {δ³¹P +63.3 ppm; P2₁/n; Z = 4; R₁ = 0.067}, 2 b {δ³¹P +63.3 ppm; P2₁/c; Z = 4; R₁ = 0.063}, 3 {δ³¹P +58.2 ppm; C2/c; Z = 4; R₁ = 0.037} and 4 {δ³¹P +58.1 ppm [18]} exist as cyclic 3-imino-2λ³σ²-phosphapropenylamides and -propenylamine, respectively, in solution as well as in the solid state. Unlike hydrogen derivative 4 the bis[N-(trimethylsilyl)iminobenzoyl]phosphanide fragments N,N′-coordinating either a lithium or a zinc cation are characterized by almost completely equalized bond lengths; typical mean distances and angles are: PC 180.3 and 178.7; CN 130.5 and 131.8; N–Si 175.3 and 179.3; N–Li 202.3; N–Zn 203.5 pm; CPC 108.8° and 110.5°; PCN 130.9° and 132.9°; CN–Li 113.0°, CN–Zn 117.4°; N–Li–N 104.6°; N–Zn–N 108.8°. Alterations in the shape of the six membered chelate rings, caused by an exchange of the 3-imino-2λ³σ²-phosphapropenylamide or related 2λ³σ²-phospha-1,3-dionate units for the corresponding phosphorus free ligands, are discussed in detail. The results of quantumchemical DFT-B3LYP calculations coincide very well with the experimentally obtained findings.