P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri- and Tetraphosphanes

[L_C^RP((PhP)₂C₂H₄)][OTf] ( 4 a,b [OTf]) and [L_C^iPrP(PPh₂)₂][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [L_C^RP(pyr)₂][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; L_C^R=1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C₂H₄P(H)Ph) and Ph₂PH. A stepwise double P−N/P−P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph₂P)₂(L_C^MeP)₂][OTf]₂ ( 7 a [OTf]₂) is observed when reacting 3 a [OTf] with diphosphane P₂Ph₄. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH₃CN)₄]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph₂PPL_C^iPr)Au}₄][OTf]₄ ( 9 [OTf]₄) was unexpectedly formed as a result of a chloride-induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH₃CN)₃][OTf]₂ (M=Cu, Ag) ( 10 [OTf]₂, 11 [OTf]₂).     

P,S-Ligands. Complexes ofP,P,P′,P′-tetraphenylethylenediphosphine monosulfide with PdCl2

1:1 and 1:2 complexes of Ph₂P(CH₂)₂P(S)Ph₂ with PdCl₂ were synthesized. Their structures were established by³¹P NMR and IR spectroscopy and X-ray diffraction analysis. In the crystals, the 1:1 complex has a chelate structure. In CH₂Cl₂, this complex partially dissociates at the Pd-.S=P bond. According to the X-ray diffraction data, only the P^III atoms the cationic chelate complex [Pd(Ph₂P(CH₂)₂P(S)Ph₂)₂]²⁺ 2NO₃ ⁻. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1122–1127, June, 2000.     

萃取剂P204与P350分离的研究与应用

研究了P204与P350混合物的分离方法, 采用烧碱热水法分离获得成功, 该方法利用烧碱与P204皂化反应形成钠盐, 而P350不与烧碱反应. 用热水洗涤分离P204与P350, 并应用于生产实践中, 从混合有机相中回收了纯P204和P350, 获得一定的经济效益.     

Synthesis of Organophosphorus Compounds with ‒P˭P≡ and ‒P˭S˭ Units

Abstract

The lithium phosphide tetrahydrofurane complexes 1 react with phosphinic acid chlorides (2) to yield diphosphenes (4), possessing a tri- and a quinquevalent phosphorus atom; the diphosphane oxides 3 are regarded to be intermediate steps of the transformation.     

P Table元素周期表简介

元素的性质一直是中学化学教学的重点内容,而这部分内容头绪多且零乱的特点也使其成为教学难点之一。因此,设计一个既能直观反映元素周期律的主要内容,又能表达各元素的特性及相关元素之间的性质差异,且适合中学生化学学习需要的元素周期表则成了广大化学教育工作者所追求的目标之一。     

Tetra-nuclear copper complex having P–N–P ligand to P–O–P ligand – synthesis,structural, and mechanistic studies

We report the synthesis and structures of three copper(I) complexes, [Cu₄(μ₃-Cl)₂(μ₂-Cl)₂{μ₂-(2,6-Me₂C₆H₃N(PPh₂)₂)}₂] (2), [Cu₄(μ₃-Cl)₂(μ₂-Cl)₂{μ₂-(Ph₂POPPh₂)}₂] (4), and [Cu₂(μ₂-Cl)₂(μ₂-PPh₂OPPh₂)(η¹-Ph₂PP(=O)Ph₂)(PPh₃)] (5), and one cobalt complex, [(CoCl₂){μ₂-2,6-Me₂C₆H₃N(PPh₂)₂}₂][CoCl₃NH₂(2,6-Me₂Ph)] (3). Tetra-nuclear copper complex 2 was prepared in good yield by the reaction of bis(diphenylphosphino)-2,6-dimethylaniline [2,6-Me₂C₆H₃N(PPh₂)₂] (1) with copper(I) chloride along with triphenylphosphine in methanol. Adding a calculated amount of water and dichloromethane mixture (1?:?10) to 2 produced a second tetra-nuclear copper(I) complex, 4, with a P–O–P backbone, along with a small amount of the unsymmetrical copper(I) complex 5. The cobalt complex 3 was obtained by reaction of 1 with cobalt(II) chloride. The solid-state structures of 2–5 were established by single-crystal X-ray diffraction analysis. In the solid state, both 2 and 4 form a tetra-nuclear copper core. In the ³¹P{¹H} NMR study, we observed the conversion of 2, with P–N–P backbone, to 4, with P–O–P backbone.     

Simple Synthesis of P1P2-Diadenosine 5′-Pyrophosphate

Pyrophosphate-linked coenzymes play essential roles in several biochemical systems. Symmetrical diadenosine-5′-pyrophosphate (Ap2A) has been synthesized from adenosine-5′-phosphate in virtually quantitative yield. The simple procedure is carried out in anhydrous pyridine using adenosine phosphoromorpholidate and adenosine monophosphate bis-(tri-n-butylammonium salt) as coupling reagents.     

浅谈P4的生长

P_4(白磷的分子式)及其衍生物的结构是化学竞赛的热点之一。本文简介了P_4的生长,对近年与本知识相关的几道竞赛题进行了解析,并提出了几点教学建议。     

磷原子团簇同分异构体的理论研究I:P5+、P5-和P5的预测

由激光产生的磷原子团簇正离子的质谱图中呈现很强的 P5 和 P5- 谱峰。使用分子图形学方法设计出 9种可能的同分异构体 ,对其中性及正负离子分子进行了分子力学、PM3半经验量子化学和 ADF密度泛函优化。在磷原子团簇模型中 ,磷原子采用 2、3或 4配位方式成键。从各异构体成键能量的比较可得知 ,最稳定的 P5 构型是四方锥的结构 ,最稳定的 P5-构型是平面五边形的结构 ,而最稳定的 P5构型是在最稳定的 P4的增加一个 2配位原子所生成的结构     

用反相高效液相色谱法测定小鼠心肌、骨骼肌中AT P、AD P和AM P的含量

采用反相高效液相色谱法同时测定小鼠心肌、骨骼肌组织中ATP(三磷酸腺苷 )、ADP(二磷酸腺苷 )、AMP(一磷酸腺苷 )的含量。以150mmol/L磷酸二氢钾缓冲液 (pH=6.25)为流动相 ,采用BDShypersilC18 不锈钢色谱柱 ,紫外检测波长为254nm ,线性范围为1～200mg/L。ATP、ADP和AMP的平均加标回收率均在90 %以上 ,检出限分别为10ng、10ng、15ng。该法灵敏、准确 ,试剂费用低。     

Uniconazole—P的合成

对氯苯甲醛与α－三唑基频哪酮在ＫＦ／Ａｌ２Ｏ３／ＰＥＧ４０００存在下经Ｋｎｏｅｖｅｎａｇｅｌ反应得８５％烯基三唑酮（Ⅱ）（Ｅ／Ｚ＝０．６５），Ⅱ经光异构化得９２％Ｅ－Ⅱ（Ｅ／Ｚ≥９９／１）；Ｅ－Ⅱ在手性相转移催化剂的存在下进行选择性不对称还原得９２％Ｕｎｉｃｏｎａｚｏｌｅ－Ｐ（Ⅰ），ｅｅ＝３０％，Ｅ／Ｚ≥９９／１．Ⅰ是高效的植物生长延缓剂．     

P,P,P'''',P''''-四氯联苯二膦的合成

芳环的二氯膦化产物是有机合成中的重要中间体，广泛应用于不对称合成领域制备手性膦配体，紫外光固化领域合成膦酰氧光引发剂等。文献报道的芳环二氯膦化方法有如下几种：(1)由芳基溴制备格氏试剂或由芳基溴直接锂化，然后与三氯化膦反应。(2)由芳基溴经格氏试剂或直接锂化，然后与二(二乙胺基)氯化膦反应，最     

薄层色谱法分离镧系元素P204—P507体系的研究

近年来,由于薄层色谱在分离稀土上所具有的优点,不断受到人们的重视。有关薄层色谱法分离稀土元素的论文也有不少报道,其中Specker等人的工作最有成效,在核裂变产物中分离了镧系元素,国内有罗焕光等人利用P_(538)体系对分离镧系元素作了研究,宗巍等人用P_(204)体系分离测定了独居石中的轻稀土元素。我们利用二-(2-乙基己基)磷酸酯(P_(204))—2-乙基已基(2-     

混合萃取剂中P204和P350的同时测定

工业萃取剂 P2 0 4 和 P350 的主要成分分别为二 -( 2 -乙基己基 )磷酸 ( D2 EHPA)和甲基膦酸二 - ( 1 -甲基庚酯 ) ( DHMP) ,两者的结构式如下 :( CH2 ) 3CH3 CHC2 H5CH2OPOOHOCH2CHC2 H5( CH2 ) 3CH3( CH2 ) 5CH3 CHCH3OPOCH3OCH-CH3( CH2 ) 5CH3( D2 EHPA)　　　　　　　　　　 ( DHMP)从以上的结构式可知 ,D2 EHPA为酸性磷类萃取剂 ,DHMP为中性膦类萃取剂。由于 P2 0 4 和 P350 具有良好的协萃效应 ,因而在湿法冶金工艺中两者常互为协萃剂组成协萃体系用于金属离子的萃取分离。P2 0 4 和 P350 单一组…     

P538与P204从盐酸介质中萃取Fe（Ⅲ）

P538 P204及其混合物从盐酸溶液中萃取Fe(Ⅲ)的平衡可分别表达为: P538: Fe~(3 ) 4/j(H_2A)j(o) K′_A Fe(HA)_3·H_2A(o) 3H~ P204: Fe~(3 ) 2H_2B_2(o) K′_B FeB_3·HB(o) 3H~ P538 P204:Fe~(3 ) 2/j(H_2A)j(o) H_2B_2(o) K′_(AB) Fe(HA)_2B·HB(o) 3H~ 其表观萃取平衡常数分别为 lgK_A=4.46±0.09 lgK_B=3.44±0.08 lgK_(AB)=5.47±0.10 等摩尔的P538,P204混合物有最大的协同萃取系数。     

Palladium complexes of P,P and P,S type bidentate ligands: Implication in Suzuki–Miyaura cross-coupling reaction

New palladium complexes of the type [PdCl₂(η²–P∩P)] (1a,1b) and [PdCl₂(η²–P∩S)] (1c,1d) have been synthesised by the reaction of PdCl₂ with P,P and P,S type bidentate ligands in 1:1 mol ratio, where, P∩P = 9,9–dimethyl-4,5-bis(diphenylphosphanyl) xanthene {Xantphos}(a) or bis(2-diphenylphosphanylphenyl)ether{DPEphos}(b); P∩S = 9,9-dimethyl-4,5-bis(diphenyl -phosphanyl) xanthenemonosulfide {Xantphos(S)}(c) or bis(2-diphenylphosphanyl phenyl) ether monosulfide {DPEphos(S)}(d). The complexes are characterized by elemental analyses, mass spectrometry, ¹H, ¹³C and ³¹P NMR spectroscopy together with the single crystal X-ray structure determination of 1a and 1d. The palladium atom in all the complexes occupies the centre of a slightly distorted square planar environment formed by a P atom, a P/S atom and two Cl atoms. The catalytic activities of 1a–1d investigated for Suzuki–Miyaura cross-coupling reactions at room temperature exhibit higher yield of the coupling products than catalysed by PdCl₂ itself. Among 1a–1d, the palladium complexes of bidentate phosphine (1a, 1b) show higher efficacy than their monosulfide analogues (1c, 1d). However, the recycling experiments with the catalysts for a selected coupling reaction between 4-bromobenzonitrile and phenylboronic acid exhibit that 1c and 1d are more efficient than 1a and 1b, which may be due to the donor effect of the P,S ligands during catalytic reaction.     

微量P204的测定

湿法冶金综合利用时,微量有机萃取剂的分析,对流程中萃取剂的损失、电解过程中的影响都有着重要的意义。P204为冶金萃取工艺流程的重要萃取剂,其常用的测定方法是测定总磷、无机磷,然后以差减法计算含量,砷高时还需分离除去。Ashbrook提出用四氯化碳在pH2.9萃取棕色的硫氰酸铁-P204络合     

Palladium complexes of P,P and P,S type bidentate ligands: Implication in Suzuki–Miyaura cross-coupling reaction

New palladium complexes of the type [PdCl₂(η²–P∩P)] (1a,1b) and [PdCl₂(η²–P∩S)] (1c,1d) have been synthesised by the reaction of PdCl₂ with P,P and P,S type bidentate ligands in 1:1 mol ratio, where, P∩P = 9,9–dimethyl-4,5-bis(diphenylphosphanyl) xanthene {Xantphos}(a) or bis(2-diphenylphosphanylphenyl)ether{DPEphos}(b); P∩S = 9,9-dimethyl-4,5-bis(diphenyl -phosphanyl) xanthenemonosulfide {Xantphos(S)}(c) or bis(2-diphenylphosphanyl phenyl) ether monosulfide {DPEphos(S)}(d). The complexes are characterized by elemental analyses, mass spectrometry, ¹H, ¹³C and ³¹P NMR spectroscopy together with the single crystal X-ray structure determination of 1a and 1d. The palladium atom in all the complexes occupies the centre of a slightly distorted square planar environment formed by a P atom, a P/S atom and two Cl atoms. The catalytic activities of 1a–1d investigated for Suzuki–Miyaura cross-coupling reactions at room temperature exhibit higher yield of the coupling products than catalysed by PdCl₂ itself. Among 1a–1d, the palladium complexes of bidentate phosphine (1a, 1b) show higher efficacy than their monosulfide analogues (1c, 1d). However, the recycling experiments with the catalysts for a selected coupling reaction between 4-bromobenzonitrile and phenylboronic acid exhibit that 1c and 1d are more efficient than 1a and 1b, which may be due to the donor effect of the P,S ligands during catalytic reaction.     

Nonbonded P···P and P···Se Interactions in Naphthalene 1,8-Positions: Role of Lone-Pair Orbitals

The lone pair-lone pair repulsion plays an important role in the nonbonded P;;;P interaction in naphthalene 1,8-positions. The conformations around P and Se in 8-(PhSe)-1-(Ph 2 P=O)C 10 H 6 are determined by the attractive O;;;Se--C 3c-4e type interaction. The P;;;Se interaction in the 1,8-positions is also discussed.     

P2(2-) and P(3-) units in the [Rh8P9]δ- polyanion of La4Rh8P9

The phosphide La(4)Rh(8)P(9) was synthesized from the elements in a bismuth flux. The structure was refined from single crystal diffractometer data: space group Cmcm, a = 1303.1(2), b = 1893.2(2), c = 576.70(6) pm, wR2 = 0.0277, 1380 F(2) values, 65 variables. The rhodium and phosphorus atoms build up a three-dimensional [Rh(8)P(9)] polyanion which leaves larger cages for the three crystallographically independent lanthanum sites. The rhodium atoms have between four and six phosphorus neighbors at Rh-P distance ranging from 229 to 254 pm. Three of the four crystallographically independent phosphorus atoms are isolated (P(3-) units), while the P4 atoms form dimers with double bond character (208 pm P-P). The P(2)(2-) diphosphenide units bond side-on to a Rh3 and end-on to four Rh5 atoms. (31)P magic angle spinning (MAS) NMR spectroscopy is able to resolve three of the four crystallographically distinct phosphorus sites. The doubly bonded phosphorus site P4 is characterized by an axially symmetric shielding tensor of moderate anisotropy Δσ = σ(33) - σ(iso) = 257 ppm. Electronic band structure calculations prove the metallic character and reveal the significant difference between the isolated P(3-) and the phosphorus atoms of the P(2)(2-) units. Magnetic susceptibility measurement reveals Pauli paramagnetism.