酸碱存在下水溶性铑膦配合物的NMR表征及氢甲酰化性能研究

31P(¹H)NMR和¹HNMR研究表明,当NaOH加入到水溶性铑膦配合物HRh(CO)·(TPPTS)₃[TPPTS:P(m-C₆H₄SO₃Na)₃]后,可观察到有少量的OTPPTS[OTPPTS:O=P(m-C₆H₄SO₃Na)₃]出现,但配合物的特征谱峰即使在高浓度的NaOH存在下也基本保持不变,表明NaOH对配合物分子结构的影响较小;当吡啶加入到HRh(CO)(TPPTS)₃中,³¹P(¹H)NMR谱图中出现游离配体TPPTS的³¹P谱峰及若干结构未知的新水溶性配合物的³¹P谱峰,表明吡啶分子将与配合物分子中的配体TPPTS发生配体交换反应.在HRh(CO)(TPPTS)₃中分别加入一定量的HCl,HNO₃,H₂SO₄和H₃PO₄等无机酸时,随着酸量的增加,配合物的³¹P物种含量逐渐下降,而OTPPTS量明显上升,直至配合物³¹P物种完全消失;高浓度乙酸对配合物结构的影响与上述无机酸类似.HRh(CO)(TPPTS)₃的1-己烯氢甲酰化催化反应结果表明,碱存在下可获得较高的正异构醛比值,但催化活性降低;酸存在下所得产物正异构醛比值相对较低且呈淡黄色.     

二苯基烷基膦-硼烷的合成

二苯基烷基膦－硼烷的合成杨文谦,黄天宝,刘玲飞,何良年,张景龄（华中师范大学有机合成研究所,武汉,４３００７０）关键词二苯基烷基膦－硼烷,三苯基膦－硼烷,合成,烷基化膦－硼烷化合物（Ｒ３Ｐ→ＢＨ３）,特别是连接不同取代基的膦－硼烷（Ｒ１Ｒ２Ｒ３Ｐ→Ｂ...     

高聚合度聚磷酸铵中特征磷的31P核磁共振分析

采用一维³¹P核磁共振(³¹P NMR)、 二维J分解谱(J-resolved)和扩散核磁(³¹P DOSY)等方法, 研究了高聚合度聚磷酸铵(APP)和多聚磷酸盐的特征磷及其偶合常数. 研究表明, 多聚磷酸盐及其中所含的二聚磷酸盐端基磷分别呈双峰和单峰特征, 多聚磷酸盐自旋偶合裂分的端基磷共振峰的偶合常数为19.4 Hz. APP中含有小分子二聚磷酸铵和正磷酸铵, 用³¹P NMR定量表征APP聚合度时需排除二聚体端基磷峰的面积. 在100 ℃水中溶解APP制备的APP水溶液中, 部分高聚合度APP发生断链, 中间磷共振峰处出现短链APP的磷共振峰.     

Conformation of N,N′-bis (2,6-dimethylmorpholino), N″-dichloroacetyl phosphoric triamide: CHCl2C(O)NHP(O)[2,6(CH3)2(NC4H6O)]2. NMR and ab initio studies

Using phosphorus pentachloride as a substrate, a new carbacyclamidophosphate, N,N″-bis (2,6-dimethylmorpholino), N″-dichloroacetyl phosphoric triamide (1) has been synthesized and characterized by ¹H, ³¹P and ¹³C NMR, IR spectroscopy and elemental analysis. Due to the presence of methyl disubstituted morpholine rings and the dichloroacetamide group, several conformers can be considered for this molecule. The ³¹P{¹H} NMR spectra for the isomeric mixture of synthesized compound showed four signals with the ratio 67.1; 19.0; 12.2; 1.7, which indicates four independent conformers. The ¹H NMR spectra confirmed these results. The conformational space and the molecular geometry of the molecule in the gaseous phase have been studied using the B3LYP method of approximation, with 6-31G and 6-311++G^** basis sets.     

高分辨NMR研究金属盐对水溶性铑膦配合物分子结构的影响

用高分辨NMR研究了NaCl、NiSO₄、CuSO₄、Fe₂(SO₄)₃和Cr₂(SO₄)₃对水溶性铑膦配合物HRh(CO)(TPPTS)₃[TPPTS;P(m-C₆H₄SO₃Na)₃]分子结构的影响.³¹P(¹H)和¹HNMR谱显示,于室温下在HRh(CO)(TPPTS)₃中加入的NaCl或NiSO₄对配合物的特征³¹P(¹H)和¹HNMR谱峰无明显影响;当加入CuSO₄后,配合物的Rh-H质子峰强度弱化明显,进而消失,且原配合物的特征磷谱峰强度减弱,新生成的磷物种谱峰逐渐成为磷谱的主要物种.当加入Fe₂(SO₄)₃或Cr₂(SO₄)₃后,三价金属离子的强顺磁性使NMR灵敏度下降,谱峰宽化,该2种盐均易与水溶性铑膦配合物产生强烈的相互作用,易使配合物特征谱峰消失.实验结果表明,上述金属盐对配合物结构破坏性大小的顺序为;Fe₂(SO₄)₃>Cr₂(SO₄)₃>CuSO₄》NiSO₄～NaCl.     

New phosphabenzenes by [4 + 2] cycloaddition of stannoles to 1-phospha-1-alkynes — determination of signs of coupling constants [J(P, C), J(P, H), J(P, Si), J(Sn, P)]

Stannoles bearing dialkylboryl groups in 3-position react with 1-phospha-1-alkynes P≡C---^tBu (1) and P≡C---CH₂^tBu (2) by [4 + 2] cycloaddition and elimination of stannylene to give phosphabenzenes in high yield. The stannylenes oligomerise to give [R¹₂Sn]_n with n ≥ 7 (R --- Me, Et, -(CH₂)₅₋ or, in the case of R¹ = ^tBu, react with the stannole itself. All phosphabenzenes are characterized by their consistent sets of NMR data. The absolute signs of the coupling constants ⁿJ(³¹P, ¹H), ⁿJ(³¹P, ¹³C), ²J(³¹P, ²⁹Si) and ²J(¹¹⁹Sn, ³¹P) were determined by appropriate ID and 2D NMR experiments.     

Zirconia-supported phosphotungstic acid as catalyst for alkylation of phenol with benzyl alcohol

The liquid-phase alkylation of phenol with benzyl alcohol was carried out using zirconia-supported phosphotungstic acid (PTA) as catalyst. The catalysts with different PTA loadings (5–20 wt.% calcined at 750 °C) and calcination temperature (15 wt.% calcined from 650 to 850 °C) were prepared and characterized by ³¹P MAS NMR and FT-IR pyridine adsorption spectroscopy. The catalyst with optimum PTA loading (15%) and calcination temperature (750 °C) was prepared in different solvents. ³¹P MAS NMR spectra of the catalysts showed two types of phosphorous species, one is the Keggin unit and the other is the decomposition product of PTA and the relative amount of each depends on PTA loading, calcination temperature and the solvent used for the catalyst preparation. The catalysts with 15% PTA on zirconia calcined at 750 °C showed the highest Brönsted acidity. At 130 °C and phenol/benzyl alcohol molar ratio of 2 (time, 1 h), the most active catalyst, 15% PTA calcined at 750 °C gave 98% benzyl alcohol conversion with 83% benzyl phenol selectivity.     

Preparation and characterization of [Re(bpy)(CO) 3L][SbF6] (L = phosphine, phosphite)

A series of rhenium complexes [fac-Re(bpy)(CO)₃L][SbF₆] (bpy = 2,2′-bipyridine, L = P(ⁿBu)₃, PEt₃, PPh₃, P(OMe)Ph₂, P(OⁱPr)₃, P(OEt)₃, P(OMe)₃, P(OPh)₃) has been prepared and characterized by the IR, UV-vis, ¹H NMR, ³¹P NMR, X-ray photoelectron spectroscopy and electrochemical techniques. Variations in the electronic properties, i.e. CO stretching, metal-to-ligand charge transfer transition, and ³¹P NMR chemical shifts were interpreted on the basis of the electron-acceptor strength of L. However, the redox potential corresponding to [Re(bpy)(CO)₃L]⁺/[Re(bpy⁻)(CO)₃L]showed ‘V-character type’ changes after the increase in the electron-acceptor strength of L. Variation of the P(2p) binding energy of the phosphorus atom indicated that the electronic structure of the coordinated phosphorus atom was strongly influenced by the electronic properties of the directly attached substituents.     

Ga改性Ga/ZSM-5分子筛的结构、 性质及其催化丙烷芳构化的固体核磁共振波谱研究

采用不同的方法制备了一系列Ga改性的ZSM-5分子筛催化剂, 通过固体核磁共振波谱(ssNMR)技术对催化剂的结构和酸性进行了表征, 并考察了其催化丙烷芳构化的性能. 结合⁷¹Ga NMR、 吸附三甲基磷(TMP)探针分子的一维³¹P 和二维(2D)¹H-³¹P HETCOR NMR实验, 发现物理混合法制备的Ga₂O₃/ZSM-5样品只含有具有较弱Lewis酸性的Ga₂O₃物种, 浸渍法制备的Ga/ZSM-5-ox和浸渍后还原再氧化法制备的Ga/ZSM-5-redo 2种样品上主要以高分散的氧化镓和阳离子Ga物种为主, 而离子交换法制备的Ga/ZSM-5-IE样品上Ga主要以阳离子Ga物种的形式存在, 高分散的氧化镓和阳离子Ga物种都具有更强的Lewis酸性. Ga/ZSM-5分子筛催化丙烷芳构化反应的结果表明, Ga物种与酸性明显影响催化剂的芳构化性能, 丙烷的转化率和芳烃的选择性顺序为 Ga/ZSM-5-IE>Ga/ZSM-5-redox>Ga/ZSM-5-ox>Ga₂O₃/ZSM-5>H-ZSM-5. 2D ¹H-³¹P HETCOR NMR实验结果表明, Ga/ZSM-5催化剂上产生的Br?nsted酸和Lewis酸(阳离子以及高分散Ga物种)的协同作用提高了分子筛的催化反应活性.     

具有生物活性的有机磷化合物研究Ⅸ．甘氨酰胺的硫代磷酰化衍生物的合成与生物活性

通过硫代磷酰-氯酯与N,N-二丙基-α-乙氨基乙酰胺反应合成了21种-α-硫代磷酰基胺基乙酰胺衍生物.所合成的化合物用元素分析、¹H NMR和³¹PNMR进行了表征,并进行了杀虫和杀螨活性的试验.     

Determination of the free activation energy for the breaking of the P---Ag bond in [(η-p-cymene)Ru(μ-pz)3Ag(PPh3)]

The Arrhenius equation corresponding to the process P---Ag+P*---Ag*→---P---Ag*+P*---Ag has been determined for [(η⁶-p-cymene)Ru(μ-pz)₃Ag(PPh₃)] (1) by complete line-shape analysis of the ³¹P NMR spectra between −40°C and +30°C. It has the form K = 10^11.8± e^{(−46±5 kJ mol−1/RT)}. The preexponential term, log A = 11.8 corresponds to a small activation entropy, whereas the activation energy, 46 kJ mol⁻¹ is comparable to those determined for other phosphorus—metal compounds.     

P NMR peak width in humate–phosphate complexes

The mobility of inorganic phosphate (P) attached to solid humic acid (HA) and fulvic acid (FA) via a metal “anchor” was investigated by ³¹P NMR spectroscopy. The peak width of the ³¹P resonance was monitored as an indicator of the degree of attachment of the element to the humic matrix. The concept was demonstrated by contrasting peak widths of thoroughly dry M–HA–P complexes with those that had been allowed to absorb different amounts of moisture. It was shown that the presence of moisture, which enhances the mobility of P, results in a significant reduction of chemical shift peak width. The work was extended to comparisons between dry systems with and without metal anchors; systems with anchors consisting of different metals; systems comprising different humates and fulvates; and systems with different size fractions of a humate. It was shown that both the type of humate/fulvate, and the metal anchor used lead to different degrees of mobility within the humic matrix. It was also found that the effect of metal addition on ³¹P peak width is greater with fulvates and smaller HA fractions than with the larger HA components.     

环状核苷酸衍生物的合成

2'-O-对甲苯磺酰基-c-AMP以对甲苯磺酰氯或三苯基膦/四氯化碳作缩合剂,与不同醇或胺反座得到3',5'-环核苷酸磷酸酯或磷酰胺,以上他合物在乙二醇二甲醚中于-60°用茶化钠或蒽化钠反应可以脱去对甲苯磺酰基,同时分离了这些磷酸酯或磷酰胺的立体异构体。     

Synthesis of phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups

Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.     

烟酰胺腺嘌呤二核苷酸(NAD~+)类似物的合成及性质

合成了3种新型结构稳定的烟酰胺腺嘌呤二核苷酸(NAD~+)类似物并通过~1H NMR、~(13)C NMR、~(31)P NMR和HRMS进行了表征。NAD~+类似物经80℃加热24 h后,通过~1H NMR确认其结构稳定;通过循环伏安法(CV)测定了其电化学性质,表明其仍然具有良好的氧化还原性能。     

不同pH条件下典型有机磷核磁图谱差异性解析

液相磷-31核磁共振波谱技术(31PNMR)是当前国内外土壤有机磷(Po)分子形态表征的主流分析技术,其主要利用乙二胺四乙酸-NaOH溶液提取,然后在高pH值(pH=13)条件下采集谱图.然而,高pH值条件下P.可能水解,同时鉴于实际土壤pH值通常在6～8范围内,因此有必要探究pH值对P.核磁谱图的影响.对D-葡萄糖-...     

固体核磁共振研究碱土金属磷硅酸盐玻璃的六配位硅结构

Phosphate glass is widely used in optical applications; however, its generally low chemical stability and poor thermal mechanical properties hinder the application of phosphate glass to the rapidly evolving laser industry. The addition of a small amount of silicon can form a six-coordinate Si (Si⁽⁶⁾) network and improve the above-mentioned poor properties of phosphate glass. Therefore, it is important to characterize and understand the structural details of phosphosilicate glasses. It is difficult to investigate the glass structure because of its complicated and disordered characteristics. However, solid-state nuclear magnetic resonance (NMR) spectroscopy can provide detailed local structural information, regardless of the presence of its long-range order. To study the effect of alkaline earth metals on Si⁽⁶⁾ species formation, we prepared phosphosilicate glasses (2MO-3P₂O₅)_(1−x)·(SiO₂)_x (M = Ca, Sr, Ba) by conventional melt-quenching, and the glass structure was investigated by solid-state NMR and Raman spectroscopy. The ³¹P and ²⁹Si NMR spectra indicated that the glass networks consisted of P⁽²⁾ and P⁽³⁾ tetrahedrons linked via four- and six-fold coordinated silicon units (Si⁽⁴⁾ and Si⁽⁶⁾). The fraction of six-coordinated silicon Si⁽⁶⁾ decreased with increasing SiO₂ content. Similarly, the Raman spectra showed that the vibration band of the P＝O stretching mode in P⁽³⁾ linked with Si⁽⁶⁾ neighbors reduced as the silica content increased. The connectivities between various phosphorus species were probed by ³¹P one- and two-dimensional refocused INADEQUATE experiments. This experimental technique is based on homonuclear J-coupling and yields correlation peaks between nuclei engaged in P―O―P linkages (P⁽²⁾ and P⁽³⁾ units). The signals from isolated ³¹P nuclei are suppressed because of the absence of J-coupling, which precludes the formation of double quantum coherences. The results indicated the segregation of P⁽²⁾ and P⁽³⁾ units in the prepared glass, which were also compared with those in the previously reported Na₂O-P₂O₅-SiO₂ glasses. They differed from alkali phosphosilicate glasses, where each P⁽³⁾ unit exhibited a maximum average of one Si⁽⁶⁾―O―P⁽³⁾ linkage, and in the alkaline earth phosphosilicate glasses, the average was approximately 0.4–0.7. When the content of Si⁽⁶⁾ units reached its maximum, further increase in the SiO₂ content did not increase the Si⁽⁶⁾ content, and the surplus Si were present as Si⁽⁴⁾. Alkaline earth metal ions exhibit weaker stabilizing effects for Si⁽⁶⁾ species. Based on the results presented herein, we constructed sketches to illustrate the local structural organization of the glass. The relationships between the compositions and structures are important for glass composition and property design. It is important to improve the performance of phosphate glass by changing its composition, particularly for large laser device applications.     

可充电池的磁共振研究

快速增长的对安全能源的需求,促使科研工作者不断探索高能量密度的可充锂离子电池(LIBs)。发展原位表征技术能更好地研究电池工作中的锂离子镶嵌机制和电池失效因素。固体核磁共振(NMR)能有效的测试短程化学环境:通过对~1H、~(6,7)Li、~(11)B、~(13)C、~(17)O、~(19)F、~(23)Na和~(31)P等同位素来探测电池材料的微观结构。除了魔角旋转(MAS)高分辨NMR谱图研究电池材料的精细结构之外,核磁共振还能无损地捕获、研究电池材料在充放电循环中的演化。因此,原位核磁共振NMR及成像(MRI)可拓展到电池充放电循环中的锂离子的动态演化以及锂离子浓度的时空分布信息。互为补充地,电子顺磁共振(EPR)及成像(EPRI)能有效地跟踪和捕获电极过渡金属、阴氧离子(O_2~(n-))的氧化还原过程。这些实时捕获的动态信息能更好地指导电极材料的构效、微观设计和电池组装的改进,最终获得优异的电化学性能。     

Syntheses, crystal structure and ab initio calculations of two new phosphoric triamides

The reaction of N-benzoylphosphoramidic dichloride with piperidine and 4-methylpiperidine lead to PhC(O)N(H)P(O)R₂ with R=piperidine (1) and R=4-methylpiperidine (2) as N-benzoyl-N′,N″-bis(piperidine) phosphoric triamide and N-benzoyl-N′,N″-bis(4-methylpiperidine) phosphoric triamide, respectively. The products have been characterized by ¹H, ¹³C, ³¹P NMR spectra, and by elemental analysis. The crystalline solid for (1) and (2) consists surprisingly of four and two independent molecules, respectively. There is a disorder in one amine group due to ring inversion in each conformer in compound 1. In the solid state, comparable magnitudes for the stabilization of the stable conformers for the more or less discrete molecules, the polarization effects, hydrogen bonding and the packing effects could be anticipated.

The geometry of compound (1) optimized by density functional calculations at the B3LYP/6-31++G* (d,p) level, is in good agreement with data obtained from X-ray crystallography.     

新型P－N－Si无卤阻燃剂的合成及其在棉纤维中的应用

以二氯磷酸苯酯(1)和γ-氨丙基三乙氧基硅烷(2)为原料,合成了一种新型的P－N－Si三元无卤阻燃剂--苯氧基-双-(三乙氧基硅丙基)磷酰胺(3),其结构经¹H NMR, ³¹P NMR和FT-IR表征。研究了溶剂,反应温度,反应时间,投料比r［n(2) : n(1)］和缚酸剂对3产率的影响。结果表明:在最佳合成条件［THF为溶剂,三乙胺为缚酸剂,1 8 mmol, r=2.4,于40 ℃反应6 h］下, 3的产率为88.2%。利用TGA测试了3的阻燃性能。结果表明：3的初始分解温度为150 ℃, 600 ℃残炭为14.6%。3在棉纤维(c)中的添加量为15%(质量百分数,即c-3¹⁵)时,600 ℃残炭为33.4%,高于c(7.6%)。