Transformation of white phosphorus in the coordination sphere of nickel complexes with σ-donating ligands

Oxidation of white phosphorus in the coordination sphere of the nickel(ii) complex with 1,1,1-tris(diphenylphosphinomethyl)ethane and 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) was shown to be possible and accompanied by the transformation of P₄ into the -P₃ ligand. The change in the nickel state was monitored by cyclic voltammetry, ³¹P NMR spectroscopy, ESR, and IR spectroscopy.     

Synthesis of New Phosphines and P-Heterocycles from Phosphonates Containing Allyl Group

Addition of phenylphosphine to allylphosphonate followed by reduction of the resulting diphosphonate gives a new branched phosphine, bis(3-phosphinopropyl)phenylphosphine. Its reaction with paraform and p-toluidine yields oligomeric 3-[3-(propylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3,7-diazadiphosphacyclooctane. Diethyl (5-allyl-2-ethoxybenzyl)phosphonate was obtained. Its reduction gives unsaturated (5-allyl-2-ethoxybenzyl)phosphine. This product adds two moles of formaldehyde to give bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine. The reaction of this compound with p-toluidine yielded, depending on the conditions, the corresponding bis(aminomethyl)phosphine, 1,3,5-diazaphosphorinane, and 1,5,3,7-diazadiphosphacyclooctane, and also their derivatives containing allyl substituents.     

One‐Pot Synthetic Route to a Class of Polydental Pyridylphosphines

Abstract

A one‐pot synthetic route is presented for convenient preparation of di‐2‐pyridylphenylphosphine (Py₂PPh, 1), di[(2‐pyridyl)phenylphosphino]methane (DPyPM, 2), and two new, long‐chain polydental pyridylphosphines: di[2‐(6‐diphenylphosphino)pyridyl]phenylphosphine (P₃N₂, 3) and bis[2‐(6‐diphenylphosphinopyridyl)phenylphosphino]methane (P₄N₂, 4).     

Phenylated polyimides: Diels-Alder reaction of biscyclopentadienones with dimaleimides

A series of phenylated polydihydrophthalimides has been synthesized by the Diels-Alder reactions of 3,3′-(oxydi-p-phenylene)bis(2,4,5-triphenylcyclopentadienone) and 3,3′-(p-phenylene)bis(2,4,5-triphenylcyclopentadienone) with N,N′-o-, -m-, and -p-phenylenedimaleimide. The polydihydrophthalimides were soluble in dimethylformamide (DMF) and had intrinsic viscosities that ranged from 0.33 to 1.01, the polymers were dehydrogenated thermally and chemically to afford the corresponding phenylated polyphthalimides. The totally aromatic polyimides were also soluble in DMF but had intrinsic viscosities only as high as 0.41. The thermogravimetric analyses of the polyphthalimides showed breaks near 530°C in air and in nitrogen atmospheres.     

三个二羧酸配体配位聚合物的合成、结构表征和荧光性质

以羧酸配体2,2''-（1,4-亚苯基双（亚甲基））双（硫二基）二苯甲酸（H₂L¹）和2,2''-（2,3,5,6-四甲基-1,4-亚苯基）双（亚甲基）双（硫二基）二苯甲酸（H₂L²）分别与金属盐反应,通过溶剂热方法合成了3个配位聚合物：{[Ni（L¹）（H₂O）₄]·2H₂O}_n （1）、[Zn（L¹）（DMA）₂]_n （2）和[Co（L²）（DMF）₂]_n （3）,其中DMA=N,N-二甲基乙酰胺,DMF=N,N-二甲基甲酰胺。对配合物1~3进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射和固体紫外可见光谱测试和表征。单晶X射线衍射表明：3个配合物均为一维锯齿形链状结构,并通过氢键作用形成三维骨架,且配体均表现为反式构象。此外,对配合物2固态荧光性质进行了研究。     

三个二羧酸配体配位聚合物的合成、结构表征和荧光性质

以羧酸配体 2,2''-(1,4-亚苯基双(亚苯基))双(硫二基)二苯甲酸(H₂L¹)和 2,2''-(2,3,5,6-四甲基-1,4-亚苯基)双(亚甲基）双(硫二基)二苯甲酸(H₂L²)分别与金属盐反应,通过溶剂热方法合成了 3个配位聚合物：{[Ni(L¹)(H₂O)₄]·2H₂O}_n (1)、[Zn(L¹)(DMA)₂]_n(2)和[Co(L²)(DMF)₂]_n (3),其中DMA=N,N-二甲基乙酰胺,DMF=N,N-二甲基甲酰胺。对配合物1~3进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射和固体紫外可见光谱测试和表征。单晶X射线衍射表明：3个配合物均为一维锯齿形链状结构,并通过氢键作用形成三维骨架,且配体均表现为反式构象。此外,对配合物2固态荧光性质进行了研究。     

Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Routes of white phosphorus activation in the coordination sphere of the nickel complexes with different ligands are shown. The first route is based on the coordination of a P₄ molecule with the metal, resulting in the deformation of the P₄ tetrahedron without destruction. This case is characteristic of the NiX₂L complexes, which are reduced at higher cathodic potentials (|E_red| > 0.9 V) (X = BF₄, Br, and Cl; L is bpy in DMF, MeCN, and acetone; 2,9-dimethyl-1,10-phenanthroline (phen) and PPh₃ in DMF and acetone). To cleave the P—P bonds in the P₄ molecule, this complex should be reduced on the electrode. The second route is the oxidation of white phosphorus in the coordination sphere of the Ni^II complex. It occurs when the complex has a sufficiently high oxidizing ability and is reduced rather easily (|E_red| < 0.9 V) (X = BF₄, L is 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) in acetone; 1,1′,5,5′-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (n²p²) in DMF; phen and PPh₃ in MeCN). The P₄ molecule opening is observed to form a new Ni^I complex containing the (P₃) fragment, for example, [(triphos)Ni(P₃)Ni(triphos)](BF₄)₂. Dedicated to the Academician V. I. Minkin on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 919–924, April, 2005.     

New aminomethylphosphines with cyanophenyl substituents at the nitrogen atoms

A condensation of bis(hydroxymethyl)arylphosphines with 3- and 4-aminobenzonitriles leads to the corresponding 3,7-diaryl-1,5-bis(cyanophenyl)-1,5-diaza-3,7-diphosphacyclooctanes. Acyclic (aryl)bis[N-(2-cyanophenyl)aminomethyl]phosphines are formed in the case of 2-aminobenzonitrile. Molecular and crystalline structure of the compounds obtained was studied by X-ray diffraction analysis.     

Synthesis and polymerization of novel formamidinium salts: A new pathway to polyamides derived from aromatic diamines

A new polycondensation pathway has been developed for the preparation of polyamides at high temperatures. p-Phenylenediamine was converted to N,N-p-phenylene bis(N′,N′-dimethylformamidine) (I), which formed 1–1 and 2–1 salts with terephthalic and adipic acids, respectively: Dicarboxylate salts were polymerizable by heating in bulk or suspension. Low-molecular-weight poly(p-phenyleneterephthalamide) was obtained from N,N-p-phenylene bis(N',N'-dimethylformamidinium) terephthalate above 225°C. The low degree of polymerization was due to terephthalic acid sublimation as well as to the well-known intractability of poly(p-phenyleneterephthalamide). High-viscosity poly(p-phenyleneadipamide) was obtained from N,N-p-phenylene bis(N′,N′-dimethylformamidinum hydrogen adipate) above 200°C. Both salts liberated dimethylformamide (DMF) during polymerization. The adipate salt also released 1 mole of adipic acid during the high-temperature vacuum stage of polymerization. A polycondensation mechanism was proposed for each salt, based on thermal gravimetric analysis (TGA-MS) and infrared (IR) analyses. The hydrolysis of N,N-p-phenylene bis(N',N'-dimethylformamidine), N,N-p-phenylene bis(N',N'-dimethylformamidinium chloride), and the two dicarboxylate salts of (I) was monitored by nuclear magnetic resonance (NMR) at room temperature. The dihydrochloride salt was most resistant to hydrolysis (k_H 6.9 × 10^?9 sec^?1; relative rate 1.0) followed by (I) 7.1, terephthalate salt, 14.9, and adipate salt, 27.2. Both dicarboxylate salts possessed sufficient hydrolytic stability for use as polycondensation monomers     

Retro-Bingel reaction in the electrochemical reduction of bis(dialkoxyphosphoryl)methanofullerenes

Four steps of reduction were detected for bis(diethoxyphosphoryl)- and bis(diisopropoxyphosphoryl)methano[60]fullerenes (1, 2) and bis(diethoxyphosphoryl)methano[70]fullerene (3) by cyclic voltammetry in the o-dichlorobenzene—DMF (3 : 1, v/v)/Bu₄NBF₄ (0.1 mol L^–1) system on a glass-carbon electrode. At the first step the reversible transfer of one electron affords stable radical anions 1 and 2 (g = 1.9999, H = 1.9 G). When two electrons per molecule are transferred, the methano fragment is rapidly eliminated (retro-Bingel reaction). This process involves the step-by-step cleavage of two C—C bonds of exo-carbon with the fullerene shell in combination with the stepwise transfer of other two electrons and a proton to form finally the carbanion of the methano fragment and fullerene dianion. For all studied compounds, the elimination rate is much higher than that for bis(alkoxycarbonyl)- and dialkoxyphosphoryl(alkoxycarbonyl)methano[60]fullerenes, which makes it possible to propose bisphosphorylmethane groups as protective in synthesis of new fullerene derivatives.     

柔性配体构筑的三个构象多样的镧系羧酸配位聚合物:合成,结构和荧光性质

利用2,2''-（1,4-亚苯基）二（亚苯基）二（硫基）苯二羧酸（H₂L¹）和2,2''-（2,3,5,6-四甲基-1,4-亚苯基）二（亚甲基）二（硫基）苯二甲酸（H₂L²）2个柔性二羧酸分别与镧系金属盐反应,通过溶剂热方法合成了3个配位聚合物：{[（NH₂（CH₃）₂][Nd（L¹）₂（DMF）]·2DMF}_n（1）和{[Ln（L²）_1.5（H₂O）（DMF）₂]·2DMF}_n[Ln=Ce（2）,Pr（3）]。利用元素分析、红外、粉末X射线衍射、热重分析等对配合物进行了表征。X射线单晶衍射分析表明：3个配合物均为二维的层状结构,并且2个配体在配合物中表现出不同的构象。（L¹）^2-在配合物1中表现出顺式和反式2种构象,（L²）^2-在配合物2和3中仅表现出反式构象。此外,对配合物的热稳定性和荧光性质也进行了研究。     

Synthesis and stereochemistry of N,N’-oxy(methylene)-diphenylene-bridged polychlorinated cage-like tetracarboxylic acid imides

N,N’-[Oxy(or methylene)di-p-phenylene]bis(4,10,11,12-tetrachlorodecahydro-1H-4,10-etheno[2]-benzofuro[5,6-f]isoindole-1,3,6,8-tetraones) were synthesized by the Diels-Alder reaction of N,N’-[oxy(or methylene)di-p-phenylene]bis(endo,exo-7,8,9,10-tetrachlorobicyclo[4.4.0]deca-7,9-diene-3,4-dicarboximide) with maleic anhydride, and stereochemical structure of the products was studied.     

Unusual scission of 3,7-dichlorobisisothiazolo[4,5-b:4",5"-e]pyrazine by nucleophiles

The reaction of 3,7-dichlorobisisothiazolo[4,5-b:4",5"-e]pyrazine with MeONa in MeOH afforded 3-chloro-5,6-dimethoxyisothiazolo[4,5-b]pyrazine. The reactions of the former with benzylamine, morpholine, and aniline gave rise to the corresponding N,N"-bis(5-amino-3-chloroisothiazol-4-yl)diazenes. In the case of benzylamine, 3,7-bis(benzylamino)bisisothiazolo[4,5-b:4",5"-e]pyrazine was isolated as a by-product. The crystal structure of N,N"-bis(5-benzylamino-3-chloroisothiazol-4-yl)diazene was established by X-ray diffraction analysis.     

Thermally stable silarylene-1,3,4-oxadiazole polymers

The effects of incorporating a p-phenylene- (or m-phenylene)-1,3,4-oxadiazole fragment into the backbone of poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)], which was developed by the authors, was investigated. Bis[(p-carbohydrazidophenyl)]diphenylsilane was copolymerized with dipentachlorophenyl terephthalate or isophthalate to produce the prepolymers poly[N-(p-diphenylsilylbenzoyl)-N′N″-(terephthaloyl)-N″′-(p-benzoyl)dihydrazide] and poly[N-(p-diphenylsilylbenzoyl)-N′,-N″-(isophthaloyl)-N″′-p-(benzoyl) dihydrazide], respectively. The polyhydrazides were converted by thermal dehydration into poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)] and poly[1,4-phenyl-ene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,3,4-(oxadiazole)]. The new polymers were soluble in organic solvents. Films cast from these solutions exhibited good adhesion to glass and metal surfaces. Thermal analysis showed that the heat stability of all these polymers was about the same and that they were resistant to decomposition when heated in air to about 400°C. The results also indicated that these polymers were somewhat less heat-resistant than samples of poly-[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-]1,3,4-(oxadiazole) synthesized from bis(p-carbohydrazidophenyl)diphenylsilane and bis-(p-carbopentachlorophenoxy-phenyl)diphenylsilane.     

Disproportionation of di(α-hydroxyalkyl)phenylphosphines and their derivatives

Conclusions When di(-hydroxyethyl)phenylphosphine and tri(-hydroxyethyl)phenylphosphonium chloride are heated with a mixture of acetic anhydride and acetic acid, they disproportionate to form 5-phenyl-2,4,6-trimethyl-1,3,5-dioxaphosphinane. Under the same conditions, di(hydroxymethyl)-phenylphosphine and di(-hydroxyethyl)phenylphosphine oxide are acetylated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 866–869, April, 1979.     

Studies on the thermotropic liquid-crystalline polymer. VIII. Synthesis and properties of fully aromatic poly(ester)s and poly(amide-ester)s containing p-phenylene diacrylic group

Three series of polymers containing p-phenylene diacrylic group were prepared by direct polycondensation in the presence of diphenylchlorophosphate and pyridine. Series I was prepared from p-phenylene bis(acrylic acid) with various hydroquinones. Series II was prepared from p-phenylene bis (β-cyano acrylic acid) with methylhydroquinone. Series III was prepared from 3-methyl-4-aminophenol with p-phenylene bis(acrylic acid) or p-phenylene bis(β-cyano acrylic acid), respectively. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). It was found that these polymers, except IIIb , exhibit thermotropic liquid-crystalline properties and show threaded or Schlieren texture under the optical polarizing microscopic observation. Furthermore, the melting temperatures of these polymers were decreased in the range of 254–354°C by incorporating with p-phenylene diacrylic group into the main chain. © 1993 John Wiley & Sons, Inc.     

Microwave‐assisted synthesis and characterization of heterocyclic,and optically active poly(amide‐imide)s incorporating L‐amino acids

N,N′‐Pyromelliticdiimido‐di‐L ‐alanine ( 1 ), N,N′‐pyromelliticdiimido‐di‐L ‐phenylalanine ( 2 ), and N,N′‐pyromelliticdiimido‐di‐L ‐leucine ( 3 ) were prepared from the reaction of pyromellitic dianhydride with corresponding L ‐amino acids in a mixture of glacial acetic acid and pyridine solution (3/2 ratio) under refluxing conditions. The microwave‐assisted polycondensation of the corresponding diimide‐diacyl chloride monomers ( 5–7 ) with 4‐phenyl‐2,6‐bis(4‐aminophenyl) pyridine ( 10 ) or 4‐(p‐methylthiophenyl)‐2,6‐bis(4‐aminophenyl) pyridine ( 12 ) were carried out in a laboratory microwave oven. The resulting poly(amide‐imide)s were obtained in quantitative yields, and they showed admirable inherent viscosities (0.12–0.55 dlg^?1), were soluble in polar aprotic solvents, showed good thermal stability and high optical purity. The synthetic compounds were characterized by IR, MS, ¹H NMR, and ¹³C NMR spectroscopy, elemental analysis, and specific rotation. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of Macroheterocycles by Reaction of N,N′-(1,4-Phenylene)bis[N′-(4,4-diethoxybutyl)urea] with Resorcinol and Its Derivatives

An efficient procedure has been developed for the synthesis of macroheterocycles by acid-catalyzed reaction of N,N′-(1,4-phenylene)bis[N′-(4,4-diethoxybutyl)urea] with resorcinol, 2-methylresorcinol, and pyrogallol. The structure of the isolated compounds was proved by spectral methods.

     

金属离子导向自组装的磺酰化对氨基苯甲酸配合物的合成与表征

用普通溶液法合成了4个配合物：[Cu（Ts-p-aba）₂（phen）（H₂O）]_n（1）、[Zn（Ts-p-aba）₂（phen）（H₂O）]·H₂O（2）、[Pb（Ts-p-aba）₂（phen）]2（3）和{[Pb（Ts-p-aba）（phen）（NO₃）]（DMF）}_n（4）（Ts-p-aba=N-对甲苯磺酰对氨基苯甲酸,phen=菲咯啉,DMF=N,N-二甲基甲酰胺）。X-射线单晶衍射结果表明：配合物1和2均为三斜晶系,P1空间群。配合物1的中心铜离子处于变形的八面体配位环境,并通过配体N-对甲苯磺酰对氨基苯甲酸扩展为一维直线链结构;配合物2是个单核分子,锌离子的配位多面体为四角锥体。配合物3和4均为单斜晶系,P2₁/c空间群。配合物3由配体N-对甲苯磺酰对氨基苯甲酸桥联成二聚体,铅离子处于变形的八面体配位环境;配合物4是具有一维链状结构的配位聚合物,铅离子处于变形的一面心八面体配位环境。另外,对4个配合物的热稳定性、电化学性能和荧光性质也进行了研究。     

Melt-processable oligoamides having internal acetylene groups in the backbone,and thermally stable polyamides therefrom

Aromatic oligoamides of DP = 5 and 11 that have all meta-phenylene linkages were prepared by controlling the ratio of isophthaloyl chloride and diamines [m-phenylenediamine and bis(3-aminophenyl)acetylene], and then end-capped with aniline or 2-aminobiphenylene. Aromatic oligoamides having para-phenylene linkages were also prepared similarly using terephthaloyl chloride as a monomer. The oligoamides that have all m-phenylene linkages were soluble in organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide, though the oligoamides having p-phenylene linkages were much less soluble. The oligoamides having acetylene units in the backbone showed exotherm due to crosslinking. The onset of the exotherm appeared at 310-340°C for the oligoamides having all m-phenylene linkages, and 330-370°C for the oligoamides having p-phenylene linkages. They were melt-processed at 350 or 380°C for 1 h, giving tough and insoluble films from oligoamides having all m-phenylene linkages and brittle films from oligoamides having p-phenylene linkages. The films showed excellent thermal properties. For example, viscoelastic analyses showed little decrease of mechanical property up to 370°C, and T_g was not observed below the temperature. Thermogravimetric analyses also showed that thermal stability of the melt-processed films were excellent. © 1992 John Wiley & Sons, Inc.