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     

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.     

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.     

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.     

[Si,N,N,P]体系异构体结构与稳定性

在B3LYP/6-311G(d)和QCISD(t)/6-311+G(2df)(单点)水平下计算得到了[Si,N,N,P]体系势能面上的一些驻点, 研究了异构体之间的异构化过程, 并讨论了该体系异构体的结构与稳定性. 结果表明在[Si,N,N,P]体系中的11个异构体中只有含有Si-P交叉成键的类蝶型四元环异构体SiNPN(E1, ²A″)是稳定的, 其他异构体由于易于重排或是解离, 稳定性较低. 研究同时给出了E1的电子与几何结构、振动频率及指认、偶极矩和转动常数等相关数据. 分析结果表明通过中间体E3(SiNPN)的反应SiN(²Π) + PN(¹Σ)→E1是由SiN(²Π)和PN(¹Σ)碎片产生E1的最有利途径, 因此E1可成为星际观测的目标. G2级别下此反应的反应焓变为215.25 kJ/mol (298.15 K), 而异构体E1在298.15 K下的标准生成焓为457.99 kJ/mol.     

电感耦合等离子发射光谱法测定镍铁中Si,Mn,P,Ni

建立ICP–AES法测定新型材料镍铁中的Si,Mn,P,Ni元素的方法。考察了镍铁基体和共存元素对测定结果的影响。通过基体匹配消除基体干扰,确定各待测元素谱线为Mn 293.930 nm,P 178.280 nm,Ni 231.604 nm,Si251.611 nm。Si,Mn,P,Ni的检出限分别为0.06,0.04,0.08,0.04 mg/L,测定结果的相对标准偏差均小于5%(n=11),加标回收率在95%~105%之间。该方法操作简便、测定结果准确可靠,可用于镍铁中Si,Mn,P,Ni的含量测定。     

15N, 31P,and 13C NMR Spectroscopy of N-Arylsulfonyl-and N-Arylcarbonyl-P,P,P-triphenylphospha-λ-Azenes. Substituent Effects and Electronic Structure

Abstract

The ¹⁵N, ³¹P and ³¹C NMR spectra of several series of phospha-λ⁵-azenes are reported. For the N-arylsulfonyl-P,P,P-triphenylphospha-δ⁵-azene series (R-C₆H₄N-SO₂-PPh₃), the ³¹P chemical shifts, various ¹³C chemical shifts and ¹J_PN were observed to correlate linearly with the Hammett σ constants. Interestingly, the ¹⁵N chemical shifts did not correlate acceptably with any σ or with the Taft dual substituent parameter equation, and 1J_PC was invariant with substituent. For the N-arylcarbonyl-P,P,P-triphenylphospha-λ⁵-azene series (R-C₆H₄-CO-N=PPh₃), δ_31P and various δ_13C's were observed to linearly correlate with the δ constants, while δ_15N, ¹J_PN and ¹J_PC correlated with both the σ and σ constants. For the N-phenyl-P,P,P-triarylphospha-λ⁵-azene series [Ph-N=P(C₆H₄-R)₃] the best correlations were observed between ³¹P, ¹⁵N and several ¹³C chemical shifts and the σ constants.     

[C, N, N, P]体系异构体结构与稳定性

在B3LYP/6-311G(d)和QCISD(t)/6-311+G(2df)水平下计算得到了[C, N, N, P]体系的9个异构体、20个过渡态及一些相关的解离碎片, 并研究了异构体之间的异构化过程, 讨论了该体系异构体的结构与稳定性. 结果表明在得到的9个异构体中, 具有2A′电子态的、非线型链状NCNP, NCPN, CNPN和CNNP 4个异构体是较稳定的. 其余异构体由于易于重排或是解离, 稳定性较低. 研究同时给出了这4个异构体的振动频率、转动常数、偶极矩、第一绝热电离能和绝热电子亲合能等相关数据, 为可能的实验和星际光谱观测提供相关的理论数据. 得到的计算结果与等价电子体系SiNNP进行了比较.     

海带细胞壁及细胞壁多糖中Sr,Ca,Mg,P分布

对海带细胞壁及细胞壁中的藻酸盐、褐藻糖胶、纤维素等多糖类物质中的Ｓｒ、Ｃａ、Ｍｇ、Ｐ含量作了ＩＣＰ－ＡＥＳ测定。结果显示，海带中的锶主要位于细胞壁，细胞壁中的锶主要位于揭藻糖胶。     

Reactor production of 32P for medical applications: an assessment of 32S(n,p)32P and 31P(n,γ)32P methods

The article describes a comparative study carried out on the reactor production of ³²P by two different processes, namely, ³²S(n,p)³²P and ³¹P(n,γ)³²P with a view to determine the merits and bottlenecks of each method and assess the usefulness of ³²P obtained from each of the processes. In a typical batch, 250 g of elemental sulfur when irradiated at a fast neutron flux of ~8 × 10¹¹ n cm^?2 s^?1 for 60 days, after chemical processing provided about 150 GBq(4.05Ci) of ³²P having specific activity of 200TBq(5500Ci)/mmole. On the other hand, irradiation of 0.35 g of red phosphorus at a fast neutron flux of ~7.5 × 10¹³ n cm^?2 s^?1 for a period of 60 days gave 75 GBq(2.02Ci) of ³²P of specific activity 7 GBq(190mCi)/mol^-1. While the specific activity of ³²P obtained from ³²S(n,p)³²P is superior to that obtained from the ^3lP(n,γ)³²P process, the requirement of elaborate target processing steps involving distillation and purification emerged as a deterrent that limits its widespread adaptability. Both the production routes offer ³²P of acceptable quality amenable for medical applications although their specific activity differs.     

Analysis of Lanthanide π-Complexes Containing N,P, and As Atoms

A sampling comprising 92 LnC _n H _m Q _k -complexes (Ln = Sc, Y, or lanthanides; Q = N, P, As) was used to analyze the influence of the nature, the oxidation state, and the coordination number of the central Ln atom and the nature of the Q atom on the parameters of the lanthanide action area. The effect of steric factors on the stability of complex groups and on the presence (or absence) of agostic interactions in the structures of these complexes was studied. A number of crystal structure features found previously for lanthanide -complexes of a different stoichiometric composition was confirmed for the structures of the given complexes.     

ICP—AES法检测Sr,Ca,Mg,P在海带多糖中的分布

应用ＩＣＰ－ＡＥＳ技术，检测了Ｓｒ，Ｃａ，Ｍｇ，Ｐ在海带叶状体的褐藻淀粉，藻酸盐，褐藻糖胶和纤维素等多糖中的分布，发现锶主要存在于褐藻糖胶中，而其他成分中的锶含量都较低，提示锶与维持藻体结构有关。     

1H, 13C, 31P, 15N, 17O-NMR Investigations of α-Sub-Stituted Aminophosphonates

Abstract

The reaction of aminomethanephosphonates 1 with dimctnylsulfate in dioxan leads to the crystalline methosulfates 2 (1). Deprotonation of the salts 2 with aqueous potassiun carbonate solution gives the very stable N-ylides 3 (1).     

A New Method to Synthesize the P,N-Heteromultifunctional Ligands

The nature of the highly polar P-N bond in phosphinimine makes a ligand of this kind become versatile in both coordination and organometallic chemistry.[1,2] Usually this kind of phosphinimine phosphine P,N-heterodifunctional ligands is prepared by the Staudinger reaction of azides with organophophine. Now a more mild and efficient method is provided. The product of Mannich reaction of 2-aminopyridine reacted with Ph2PCl in the presence of Et3N, giving the phosphinimine compound 1 in more than 90% yield.     

Synthesis of asymmetricP,P-dialkyl-P′,P′-diphenylethylenediphosphine dioxides

AsymmetricP, P-dialkyl-P,P-diphenylethylenediphosphine dioxides were synthesized by the addition of dialkylphosphinous acids to diphenylvinylphosphine oxide in toluene without a catalyst and in DMSO in the presence of concentrated aqueous alkali. The method for isolating dipropyl- and dibutylphosphinous acids obtained by reactions of diethylphosphite with the corresponding alkylmagnesium bromides was improved.Deceased in 1994.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 139–141, January, 1995.     

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Ｐ＾＋５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分子力学、ＰＭ３半经验量子化学和ＡＤＦ密度泛函优化。     

Si4X(X=C,N,O,Si,P,S)原子簇结构的理论研究

在密度泛函B3LYP/6-311G*水平上, 对具有C3v对称的Si4X (X = C, N, O, P, S)原子簇进行了几何构型优化计算, 并讨论它们的热力学稳定性、动力学活性、Mulliken布居、SiX键长、占据价轨道的对称性以及HOMO能级位置等周期递变规律。     

Near-saturation (P,ρ,T) and vapor-pressure measurements of NH3, and liquid-phase isothermal (P,ρ,T) and bubble-point-pressure measurements of NH3+H2O mixtures

Near-saturation pressure, density, and temperature (P,ρ,T) and vapor-pressure measurements for NH₃ are reported over a temperature range from 279 to 392 K. Liquid-phase isothermal (P,ρ,T) and bubble-point-pressure measurements for two standard mixtures of NH₃+H₂O (x_NH3=0.8360 and 0.9057 mole fraction) are reported over a temperature range from 280 to 379 K and at pressures to 7.7 MPa. These data are compared to literature data and correlations and agree within ±3% for bubble-point pressures, ±0.005 g/cm³ for liquid densities, and ±0.0011 g/cm³ for vapor densities. A consistent data set for equation-of-state optimization at high concentrations of NH₃ is proposed.