A structural hierarchy in the hydrogen‐bonded adduct N,N′‐di­methyl­piperazine–tartaric acid–water (1/2/2): an N‐component N‐dimensional structure (N = 3) with substructures having N = 1 and 2

In the hydrated adduct N,N′‐di­methyl­piperazine‐1,4‐diium bis(3‐carboxy‐2,3‐di­hydroxy­propanoate) dihydrate, [MeNH(CH₂CH₂)₂NHMe]²⁺·2(C₄H₅O₆)^?·2H₂O or C₆H₁₆N₂²⁺·2C₄H₅O₆^?·2H₂O, formed between racemic tartaric acid and N,N′‐di­methyl­piperazine (triclinic P, Z′ = 0.5), the cations lie across centres of inversion. The anions alone form chains, and anions and water mol­ecules together form sheets; the sheets are linked by the cations to form a pillared‐layer framework. The supramolecular architecture thus takes the form of a family of N‐dimensional N‐component structures having N = 1, 2 or 3.     

The reaction of 3,4‐diamino‐1,2,5‐oxadiazoles with formaldehyde

The compounds 5,6‐dihydro‐4H‐imidazo[4,5‐c][1,2,5]oxadiazole ( 3a , R?H), 4,6,10,12‐tetramethyl‐5,6,11,12‐tetrahydro‐4H,10H‐bis(1,2,5)oxadiazolo[3,4‐d:3′,4′‐I][1,3,6,8]tetraazecine ( 4b , R?CH₃), N³,N³′‐methylenebis‐3,4‐diamino‐1,2,5‐oxadiazole ( 5a , R?H) and N³,N³′‐methylenebis(N,N′‐dimethyl‐3,4‐diamino‐1,2,5‐oxadiazolee) ( 5b , R?CH₃) were synthesized from the reaction of formaldehyde with 3,4‐diamino‐1,2,5‐oxadiazole and N,N′‐3,4‐dimethylamino‐1,2,5‐oxadiazole in an acetonitrile.     

Synthesis and characterization of oxovanadium(IV), vanadium(IV) and oxovanadium(V) complexes of tetradentate Schiff bases. Attempted preparation of vanadium-carbon bonded compounds through desilylation

Condensation of 1,3-diaminopropane-2-ol with diacetylmonoxime, acetylacetone, salicylaldehyde and orthohydroxyacetophenone yielded the tetradentate Schiff bases N,N′-(2-hydroxy)propylenebis{(2-imino-3-oximino)butane} (H₂dampnol), N,N′-(2-hydroxy)propylenebis(acetylacetoneimine) (H₂acacpnol), N,N′-(2-hydroxy)propylenebis-(salicyalaldimine) (H₂salpnol) and N,N′-(2-hydroxy)propylenebis(7-methylsalicylaldimine) (H₂ohacpnol), respectively. The ligands form complexes with oxovanadium(IV), vanadium(IV) and oxovanadium(V) salts. Some mixed ligand complexes involving σ-bonded phenyl and benzyl radical along with tetradentate ligand, H₂L (where, H₂L stands for H₂dampnol, H₂acacpnol, H₂salpnol or H₂ohacpnol) of the types [(L)V(C₆H₅)₂]CH₃OH and [(L)V(CH₂Ph)₂]CH₃OH have been synthesized, characterized and also provide the syntheses of some new organovanadium(IV) complexes. Silylation coupled with desilylation have been employed as a route to new organovanadium(IV) complexes. All the complexes have been characterized with the help of elemental analyses, molar conductance values, molecular weights, magnetic moments and spectroscopic (IR, UV-Vis, ESR) data.     

Nickel(II) Complexes of Pentadentate N5 Ligands as Catalysts for Alkane Hydroxylation by Using m‐CPBA as Oxidant: A Combined Experimental and Computational Study

A new family of nickel(II) complexes of the type [Ni(L)(CH₃CN)](BPh₄)₂, where L=N‐methyl‐N,N′,N′‐tris(pyrid‐2‐ylmethyl)‐ethylenediamine (L1, 1 ), N‐benzyl‐N,N′,N′‐tris(pyrid‐2‐yl‐methyl)‐ethylenediamine (L2, 2 ), N‐methyl‐N,N′‐bis(pyrid‐2‐ylmethyl)‐N′‐(6‐methyl‐pyrid‐2‐yl‐methyl)‐ethylenediamine (L3, 3 ), N‐methyl‐N,N′‐bis(pyrid‐2‐ylmethyl)‐N′‐(quinolin‐2‐ylmethyl)‐ethylenediamine (L4, 4 ), and N‐methyl‐N,N′‐bis(pyrid‐2‐ylmethyl)‐N′‐imidazole‐2‐ylmethyl)‐ethylenediamine (L5, 5 ), has been isolated and characterized by means of elemental analysis, mass spectrometry, UV/Vis spectroscopy, and electrochemistry. The single‐crystal X‐ray structure of [Ni(L3)(CH₃CN)](BPh₄)₂ reveals that the nickel(II) center is located in a distorted octahedral coordination geometry constituted by all the five nitrogen atoms of the pentadentate ligand and an acetonitrile molecule. In a dichloromethane/acetonitrile solvent mixture, all the complexes show ligand field bands in the visible region characteristic of an octahedral coordination geometry. They exhibit a one‐electron oxidation corresponding to the Ni^II/Ni^III redox couple the potential of which depends upon the ligand donor functionalities. The new complexes catalyze the oxidation of cyclohexane in the presence of m‐CPBA as oxidant up to a turnover number of 530 with good alcohol selectivity (A/K, 7.1–10.6, A=alcohol, K=ketone). Upon replacing the pyridylmethyl arm in [Ni(L1)(CH₃CN)](BPh₄)₂ by the strongly σ‐bonding but weakly π‐bonding imidazolylmethyl arm as in [Ni(L5)(CH₃CN)](BPh₄)₂ or the sterically demanding 6‐methylpyridylmethyl ([Ni(L3)(CH₃CN)](BPh₄)₂ and the quinolylmethyl arms ([Ni(L4)(CH₃CN)](BPh₄)₂, both the catalytic activity and the selectivity decrease. DFT studies performed on cyclohexane oxidation by complexes 1 and 5 demonstrate the two spin‐state reactivity for the high‐spin [(N5)Ni^II?O^.] intermediate (ts1_hs, ts2_doublet), which has a low‐spin state located closely in energy to the high‐spin state. The lower catalytic activity of complex 5 is mainly due to the formation of thermodynamically less accessible m‐CPBA‐coordinated precursor of [Ni^II(L5)(OOCOC₆H₄Cl)]⁺ ( 5 a ). Adamantane is oxidized to 1‐adamantanol, 2‐adamantanol, and 2‐adamantanone (3°/2°, 10.6–11.5), and cumene is selectively oxidized to 2‐phenyl‐2‐propanol. The incorporation of sterically hindering pyridylmethyl and quinolylmethyl donor ligands around the Ni^II leads to a high 3°/2° bond selectivity for adamantane oxidation, which is in contrast to the lower cyclohexane oxidation activities of the complexes.     

Controlled helical orientation of carbazole in amino acid derived poly(N‐propargylamide)s

Novel L ‐alanine and L ‐glutamic acid derivatized, carbazole‐containing N‐propargylamides [N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐alanine N′‐propargylamide and N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] were synthesized and polymerized with (nbd)Rh⁺[η⁶‐C₆H₅B^?(C₆H₅)₃] (nbd = norbornadiene) as a catalyst to obtain the corresponding polymers with moderate molecular weights in high yields. Polarimetry, circular dichroism, and ultraviolet–visible spectroscopy studies revealed that both poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐alanine N′‐propargylamide] and poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] took a helical structure with a predominantly one‐handed screw sense in tetrahydrofuran, CHCl₃, and CH₂Cl₂. The helix content of poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐alanine N′‐propargylamide] could be tuned by heat or the addition of a protic solvent, and the helical sense of poly[N‐(9‐carbazolyl) ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] was inverted by heat in CHCl₃ or in mixtures of tetrahydrofuran and CH₂Cl₂. Poly[N‐(9‐carbazolyl) ethyloxycarbonyl‐L ‐alanine N′‐propargylamide] and poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] also took a helical structure in film states. They showed small fluorescence in comparison with the monomers and redox activity based on carbazole. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 253–261, 2007     

Syntheses and structures of four new mixed‐amide phosphoric triamides

Phosphoric triamides have extensive applications in biochemistry and are also used as O‐donor ligands. Four new mixed‐amide phosphoric triamide structures, namely rac‐N‐tert‐butyl‐N′,N′′‐dicyclohexyl‐N′′‐methylphosphoric triamide, C₁₇H₃₆N₃OP, (I), rac‐N,N′‐dicyclohexyl‐N′‐methyl‐N′′‐(p‐tolyl)phosphoric triamide, C₂₀H₃₄N₃OP, (II), N,N′,N′′‐tricyclohexyl‐N′′‐methylphosphoric triamide, C₁₉H₃₈N₃OP, (III), and 2‐[cyclohexyl(methyl)amino]‐5,5‐dimethyl‐1,3,2λ⁵‐diazaphosphinan‐2‐one, C₁₂H₂₆N₃OP, (IV), have been synthesized and studied by X‐ray diffraction and spectroscopic methods. Structures (I) and (II) are the first diffraction studies of acyclic racemic mixed‐amide phosphoric triamides. The P—N bonds resulting from the different substituent –N(CH₃)(C₆H₁₁), (C₆H₁₁)NH–, 4‐CH₃‐C₆H₄NH–, (tert‐C₄H₉)NH– and –NHCH₂C(CH₃)₂CH₂NH– groups are compared, along with the different molecular volumes and electron‐donor strengths. In all four structures, the molecules form extended chains through N—H…O hydrogen bonds.     

Unusual formation of a λ 6P-tetrafluorophosphate involving intramolecular donor–acceptor interaction; x-ray crystal structure analysis and temperature-dependent NMR-spectra

The N,N,N′-trimethylethylenediaminetetrafluorophosphate, 4 , was formed in the unusual reaction of N,N,N′-trimethyl-N′-trimethylsilylethylenediamine, 1 , with the N P-bonded tetrafluorophosphoranes, dimethylaminotetrafluorophosphorane, 2 , or morpholinotetrafluorophosphorane, 3 . There was no evidence for the cleavage of a P F bond in the tetrafluorophosphoranes (with formation of Me₃SiF); instead, the Si N compounds, R₂N SiMe₃ (R₂ = Me₂ or O(CH₂CH₂)₂) were formed. The ¹⁹F and ³¹P NMR spectra of 4 at room temperature indicated dynamic behavior. The X-ray crystal structure analysis of 4 revealed the presence of a five-membered ring, formally as a result of intramolecular donor–acceptor interaction (P N = 196.5 pm) between the nitrogen atom of the Me₂N group and phosphorus.     

Nitrogen-15 nuclear magnetic resonance spectroscopy. N?H proton exchange reactions of urea and substituted ureas

Proton-coupled nitrogen-15 NMR spectra of urea, N-methylurea, N,-N′-dimethylurea, N-methyl-N′-benzylurea and N-phenylurea have been obtained at natural abundance level in neutral, basic and acidic solutions at 25°C. Base-catalyzed N? H proton exchange of the ? NH₂ group of N-methylurea in water was found to be 1.5 times faster than that for the -NH- group, while the corresponding acid-catalyzed exchange is 7.5 times faster. Comparison of urea and N,-N′-dimethylurea in water shows urea to be 10 times faster in base but 2 times slower in acid. The ratio of the base-catalyzed N? H proton exchanges of the two -NH- groups of N-methyl-N′-benzylurea in dimethyl sulfoxide is close to unity, whereas the CH₃NH- group exchanges 4 times faster in acid. Similarly, the C₆H₅NH- group of N-methyl-N′-phenylurea exchanges 50 times faster than the CH₃NH- group in base and about 3 orders of magnitude slower in acid. The results are rationalized by consideration of steric and electronic effects.     

Self‐assembly of a one‐dimensional iron(II) coordination polymer with p‐phenylenebis(picolinaldimine)

catena‐Poly[[[dichloridoiron(II)]‐μ‐N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine] methanol disolvate], [FeCl₂(C₁₈H₁₄N₄)]·2CH₃OH, forms a one‐dimensional coordination polymer. The polymeric chains run parallel to the c axis. O—H...Cl—Fe and C—H...O hydrogen‐bonding interactions with methanol solvent molecules stabilize the open supramolecular framework. Each Fe^II atom adopts an octahedral geometry coordinated by four N atoms from two N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine ligands and completed by two cis Cl atoms. The compound has C₂ (and C_i) molecular symmetry, which is coincident with the crystallographic twofold symmetry at (0, y, ). The one‐dimensional structure is propagated via the crystallographic inversion center located at the benzene ring centroid (0, , 0).     

Five related N′‐(2,2,2‐trichloroethanimidoyl)benzene‐1‐carboximidamides

In the solid state, 4‐methoxy‐N′‐(2,2,2‐trichloroethanimidoyl)benzene‐1‐carboximidamide, C₁₀H₁₀Cl₃N₃O, (I), N′‐(2,2,2‐trichloroethanimidoyl)benzene‐1‐carboximidamide, C₉H₈Cl₃N₃, (II), 4‐chloro‐N′‐(2,2,2‐trichloroethanimidoyl)benzene‐1‐carboximidamide, C₉H₇Cl₄N₃, (III), 4‐bromo‐N′‐(2,2,2‐trichloroethanimidoyl)benzene‐1‐carboximidamide, C₉H₇BrCl₃N₃, (IV), and 4‐trifluoromethyl‐N′‐(2,2,2‐trichloroethanimidoyl)benzene‐1‐carboximidamide, C₁₀H₇Cl₃F₃N₃, (V), display strong intramolecular N—H...N hydrogen bonding across the chelate ring and also intramolecular N—H...Cl contacts. Additional intermolecular hydrogen bonds link the molecules into chains, double chains or sheets in all cases except for compound (V). For compound (II), there are three independent molecules per asymmetric unit.     

ORGANISCHE PHOSPHORVERBINDUNGEN 85.1 HERSTELLUNG,EIGENSCHAFTEN UND BIOLOGISCHE WIRKUNG VON N-AMINOGLYPHOSATE UND AZAGLYPHOSATE

Abstract

The synthesis and the chemical, physical and spectral properties of N-aminoglyphosate ethylester (hydrazino-N′-carbethoxymethyl-N′-methylphosphonic acid) 4a, H₂OPCH₂N(NH₂)CH₂CO₂C₂H₅, of hydrazino-N′-carbethoxymethyl-N′-methyl-P-methylphosphinic acid 4b, CH₃(HO₂)PCH₂N(NH₂)-CH₂CO₂C₂H₅, and of azaglyphosate ethylester (hydrazino-N-carbethoxymethyl-N-methyl-phosphonic acid 9, H₂O₃PCH₂NHNHCH₂CO₂C₂H₅, are described. 4a, 9 and 10 exhibit plant growth regulating properties.     

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Treatment of N,N′‐bis(aryl)formamidines (ArFormH), N,N′‐bis(2,6‐difluorophenyl)formamidine (DFFormH) or N,N′‐bis(2,6‐diisopropylphenyl)formamidine (DippFormH), with europium metal in CH₃CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)₂(CH₃CN)₂}₂] ( Eu1 ) or [Eu(DippForm)₂(CH₃CN)₄] ( Eu2 ). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg⁰. With DFFormH in CH₃CN, [{Yb(DFForm)₂(CH₃CN)}₂] ( Yb1 ) was obtained in good yield, and [Yb(DFForm)₂(thf)₃] ( Yb3 ) was obtained from a synthesis in CH₃CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare‐earth formamidinates. Heating Yb1 in PhMe/C₆D₆ resulted in decomposition to trivalent products, including one from a CH₃CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb⁰, Hg(R)₂ (R=Ph, C₆F₅), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)₂(thf)₃] ( Yb3 ), or the first five coordinate rare‐earth formamidinate complex [Yb(DippForm)₂(thf)] ( Yb4 b ), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)₃(thf)] ( Yb6 ). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl₄(thf)₂, Ph₃CCl, C₂Cl₆) gave [Yb(DFForm)₃(bp)] or [Yb(DFForm)₂Cl(thf)₂], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare‐earth ArForm complexes been achieved in Eu2 and Yb4 b , respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ‐1κ(N:N′):2κ(N:N′) in Eu1 , or the twisted μ‐1κ(N:N′):2κ(N′:F′) DFForm coordination in Yb1 , both unprecedented in divalent rare‐earth ArForm chemistry and in the wider divalent rare‐earth amidinate field.     

Two N,N′‐diaryl‐2,2,2‐trichloroethane‐1,1‐diamines: hydrogen‐bonded supramolecular structures in one and two dimensions

The molecules of 2,2,2‐trichloro‐N,N′‐diphenylethane‐1,1‐diamine, C₁₄H₁₃Cl₃N₂, are linked into (040) sheets by a combination of C—H...Cl and C—H...π(arene) hydrogen bonds. In 2,2,2‐trichloro‐N,N′‐bis(4‐methylphenyl)ethane‐1,1‐diamine, C₁₆H₁₇Cl₃N₂, the molecules are linked into C(7) chains by two independent C—H...Cl hydrogen bonds and one Cl...Cl contact.     

Mononuclear and three‐dimensional metal complexes based on a multidentate hydrazone ligand

A potentially pentadentate hydrazone ligand, N′‐[1‐(pyrazin‐2‐yl)ethylidene]nicotinohydrazide (HL), was prepared from the condensation reaction of nicotinohydrazide and acetylpyrazine. Reactions of HL with MnCl₂, Mn(CH₃COO)₂ and Cd(CH₃COO)₂ afforded three metal complexes, namely dichlorido{N′‐[1‐(pyrazin‐2‐yl‐κN¹)ethylidene]nicotinohydrazide‐κ²N′,O}manganese(II), [MnCl₂(C₁₂H₁₁N₅O)], (I), bis{N′‐[1‐(pyrazin‐2‐yl‐κN¹)ethylidene]nicotinohydrazidato‐κ²N′,O]manganese(II), [Mn(C₁₂H₁₀N₅O)₂], (II), and poly[[(acetato‐κ²O,O′){μ₃‐N′‐[1‐(pyrazin‐2‐yl‐κ²N¹:N⁴)ethylidene]nicotinohydrazidato‐κ³N′,O:N¹}cadmium(II)] chloroform disolvate], {[Cd(C₁₂H₁₀N₅O)(CH₃COO)]·2CHCl₃}_n, (III), respectively. Complex (I) has a mononuclear structure, the Mn^II centre adopting a distorted square‐pyramidal coordination. Complex (II) also has a mononuclear structure, with the Mn^II centre occupying a special position (C₂ symmetry) and adopting a distorted octahedral coordination environment, which is defined by two O atoms and four N atoms from two N′‐[1‐(pyrazin‐2‐yl)ethylidene]nicotinohydrazidate (L⁻) ligands related via a crystallographic twofold axis. Complex (III) features a unique three‐dimensional network with rectangular channels, and the L⁻ ligand also serves as a counter‐anion. The coordination geometry of the Cd^II centre is pentagonal bipyramidal. This study demonstrates that HL, which can act as either a neutral or a mono‐anionic ligand, is useful in the construction of interesting metal–organic compounds.     

Syntheses and structures of two new uranyl complexes [UO2(DPDPU)2(NO3)2](C6H5CH3) and [UO2(PMBP)2(DPDPU)](CH3C6H4CH3)0.5

Two new uranyl complexes [UO₂(DPDPU)₂(NO₃)₂](C₆H₅CH₃) (1) and [UO₂(PMBP)₂ (DPDPU)](CH₃C₆H₄CH₃)_0.5 (2), (DPDPU?=?N,N′-dipropyl-N,N′-diphenylurea, HPMBP?= 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5) were synthesized and characterized. The coordination geometry of the uranyl atom in 1 is distorted hexagonal bipyramidal, coordinated by two oxygen atoms of two DPDPU molecules and four oxygen atoms of two bidentate nitrate groups. The coordination geometry of the uranyl atom in 2 is distorted pentagonal bipyramidal, coordinated by one oxygen atom of one DPDPU molecule and four oxygen atoms of two chelating PMBP molecules.     

[Cu(phen)2(μ‐IDA)Cu(phen)](ClO4)2·CH3OH: tridentate and monodentate binding to two copper(II) species by a bridging ligand

The stoichiometric reaction of 1,10‐phenanthroline (phen), imino­di­acetic acid (IDA‐H₂) and Cu(ClO₄)₂ in a H₂O–CH₃OH (2:1) solution yields μ‐imino­diacetato‐2:1κ⁴O,N,O′:O′′‐tris(1,10‐phenanthroline)‐1κ⁴N,N′;2κ²N,N′‐dicopper(II) diperchlorate methanol solvate, [Cu₂(C₄H₅NO₄)(C₁₂H₈N₂)₃](ClO₄)₂·CH₃OH. The IDA ligand bridges the two Cu^II ions via a carboxyl­ate group and uses one further N and an O atom of the second carboxylate group to complete a fac‐tridentate coordination at one Cu centre. A phen ligand completes a distorted square‐pyramidal coordination at this metal atom, although there is weak coordination by a perchlorate O atom at a sixth position. The second Cu centre has a distorted trigonal–bipyramidal coordination to two phen moieties and a carboxyl­ate O atom.     

Synthesis and crystal structure of the dinuclear copper(II) Schiff base complex μ‐hydroxido‐μ‐chlorido‐bis{[bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine]chloridocopper(II)} dichloromethane sesquisolvate

Transition metal complexes of Schiff base ligands have been shown to have particular application in catalysis and magnetism. The chemistry of copper complexes is of interest owing to their importance in biological and industrial processes. The reaction of copper(I) chloride with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, systematic name: (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]} in a 1:1 molar ratio in dichloromethane without exclusion of air or moisture resulted in the formation of the title complex μ‐chlorido‐μ‐hydroxido‐bis(chlorido{(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}copper(II)) dichloromethane sesquisolvate, [Cu₂Cl₃(OH)(C₂₀H₁₈N₄O₄)₂]·1.5CH₂Cl₂. The dinuclear complex has a folded four‐membered ring in an unsymmetrical Cu₂OCl₃ core in which the approximate trigonal bipyramidal coordination displays different angular distortions in the equatorial planes of the two Cu^II atoms; the chloride bridge is asymmetric, but the hydroxide bridge is symmetric. The chelate rings of the two Nca₂en ligands have different conformations, leading to a more marked bowing of one of the ligands compared with the other. This is the first reported dinuclear complex, and the first five‐coordinate complex, of the Nca₂en Schiff base ligand. Molecules of the dimer are associated in pairs by ring‐stacking interactions supported by C—H…Cl interactions with solvent molecules; a further ring‐stacking interaction exists between the two Schiff base ligands of each molecule.     

New Heterocyclic Organophosphorus–Sulfur–Nitrogen Compounds,Syntheses and Structures

The new compound C₁₀H₆P(S)[NSi(CH₃)₃]₂P(S) ( 3 ) which contains a P₂N₂ heterocycle has been prepared in low yield by partial thermal decomposition of 1-{[N,N′-bis(trimethylsilyl)acetamidinium]sulfido}-3-(trimethylsilylamino)-1 H,3 H,1 λ⁵,3 λ⁵-naphtho[1,8 a,8-cd][1,2,6]thiadiphosphinine-1,3-dithione [CH₃C{NHSi(CH₃)₃}₂]⁺[C₁₀H₆P(S)(NHSiMe₃)SP(S)₂]^– ( 2 ). Reaction of 2 with potassium hydroxide in acetonitrile gives the completely desilylated product [CH₃C(NH₂)₂]⁺[C₁₀H₆P(S)(NH₂)SP(S)₂]^– ( 4 ). The structures of the new compounds 3 and 4 were elucidated by FTIR and NMR spectroscopy methods and by X-ray structure analyses.     

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.     

Heterobimetallische Komplexe von Lithium,Aluminium und Gold mit dem N‐[2‐N′,N′‐(Dimethylaminoethyl)‐N‐methyl‐aminoethyl]‐ferrocenyl‐Liganden (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}

Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with ⁿBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr₃ and AuCl · PPh₃ the heterobimetallic organo derivatives (FcN,N)AlBr₂ ( 3 ), (FcN,N)Au · PPh₃ ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.