含金属基团的四价锡化合物的合成和取代反应动力学

通式为[Fe(CO)~2Cp]~2Sn(Ar)Cl的化合物为一组新的化合物,由[Fe(CO)~2Cp]~2SnCl2与AgMgX反应合成.[Fe(CO)~2Cp]~2Sn(Ar)Cl与各种亲核试剂Y发生取代反应给出另一组新的化合物[Fe(CO)~2Cp]~2Sn(Ar)Y,其中[Fe(CO)~2Sn(p-MeC~6H~4)Br经X射线衍射分析确定结构.[Fe(CO)~2Cp]~2Sn(1,3,5-Me~3C~6H~3)Cl与NAS~2CNMe~2或KSCN在不同溶剂中的反应动力学表明,由于锡易形成高配位中间体,尽管锡上两个较大的金属基团带来一定空间障碍,反应仍主要按SN2机理进行.     

澳大利亚烟煤热解的拉曼光谱研究

采用拉曼光谱考察了澳大利亚烟煤在常压、温度为298~1 473 K条件下,不同热解气氛(Ar和N2)下的热解性能。结合AD/Aall、AG/Aall、WG以及PG-PD等表征参数分析发现,澳大利亚烟煤的热解可以分为三个阶段:298~873 K为固有小分子和大分子键能较弱处断裂分解产生的小分子化合物的析出沉积和挥发;873~1 273 K为大分子化合物裂解挥发和炭化;1 273~1 473 K为焦炭的石墨化。在N2和Ar气氛经1 473 K热处理后,焦炭的不同杂化结构的碳相对含量呈现明显差异。不同保温时间下,其煤焦碳结构演变趋势相似,但保温时间越长,越有利于小分子挥发分在较低温度的挥发。     

Synthesis and Structural Characterization of N,N-disubstituted Acylguanidines

A series of five N,N-disubstituted acylguanidines R~1C(O)N=C[N(H)R~2]NR_2~3(R~1=Mes or Ph; R~2=Ar??or Ar?; R~3=Cy, Bn, iPr, or Et)(Mes=2,4,6-Me_3C_6H_2, Ar??=2,6-iPr_2C_6H_3, Ar?=2,6-Me_2C_6H_3) was synthesized from the reactions of parent acylthioureas with respective secondary amines. According to structutral characterization by single-crystal X-ray diffraction, the rough reduction of the steric hindrance of R substitutents of R~1 C(O)N=C[N(H)R~2]NR_2~3(also abbreviated as R~1-R~2-R~3 for comparison purposes) led to the slight enlongation of N(1)–C(1) bond lengthes and small decrease of N(1)–C(1)–N(3) bond angles from Mes–Ar??–Cy(1) to Ph–Ar??–Bn(2), Ph–Ar??–iPr(3) and Ph–Ar?–Cy(4). At the same time, the N(1)–H(1)···O(1) intramolecular hydrogen bonds were observed in these cases. When R~3=Et, an interesting compound Ph-Ar?-Et(5) was obtained with the formation of intermolecular hydrogen bonds instead. 1 belongs to the monoclinic system, space group P2_(1/n) with a=9.6488(3), b=28.5318(8), c=11.9155(3) ?, b=91.439(2)o, V=3279.27(16) ?~3, and Z=4. 2 belongs to the triclinic system, space group P1 with a=9.6759(7), b=10.8613(8), c=15.7642(12) ?, a=70.429(3), b=79.257(4), g=69.052(4)o, V=1453.63(19) ?~3 and Z=2. 3 belongs to the monoclinic system, space group P2_(1/c) with a=11.1393(4), b=13.0643(4), c=17.6600(6) ?, b=101.866(2)o, V=2515.09(15) ?~3 and Z=4. 4 belongs to the monoclinic system, space group C2/c with a=17.8466(3), b=13.6126(2), c=21.6710(4) ?, b=90.7310(10)o, V=4992.72(14) ?~3 and Z=8. 5 is of orthorhombic system, space group P2_12_12_1 with a=10.5555(2), b=11.8913(2), c=14.9558(4) ?, V=1877.23(5) ?~3 and Z=4.     

芳基取代四甲基环戊二烯基铼羰基化合物的合成、晶体结构及催化性能（英文）

芳基取代的四甲基环戊二烯C5HMe4Ar(Ar=Ph,4-CH_3Ph,4-OCH_3Ph,4-ClPh,4-BrPh)分别与Re2(CO)10在二甲苯中加热回流,得到了5个单核配合物[(η5-C5Me4Ar)Re(CO)3](Ar=Ph(1),4-CH_3Ph(2),4-OCH_3Ph(3),4-ClPh(4),4-BrPh(5))。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。     

Magmatism and deformation times of the Xidatan rock series, East Kunlun Mountains

The Xidatan rock series consist of mylonite, gneiss and granite. The U-Pb age showsthat the granite was formed at 206 Ma, and the ~(40)Ar/~(39)Ar ages of the biotite display that the my-lonite was formed at 145 Ma when the Xidatan ductile shear zone occurred. At about 110-100 Mathe Xidatan Fault reactivated again. As a result, the biotite and muscovite of Xidatan rock seriesopened their argon isotope system.     

氟化电热蒸发／电感耦合等离子体原子发射光谱测定稀土元素的研究

本文采用聚四氟乙烯(PTFE)悬浮体为卤化剂,使稀土元素在石墨炉中完全蒸发,用载气(Ar)将蒸发物送入电感耦合等离子体中进行测定。此方法有绝对检出限低(达10~(-10)～10~(-12)g),无记忆效应和进样体积小等特点。     

由两相体系(C~6H~6/H~2O)合成一些新的二茂锆二芳氧基配合物的研究

本文首次报道用两相法(C_6H_6/H_2O)合成二茂锆二芳氧基配合物,并与绝对无水条件下的合成结果进行了比较,共合成了五个新的配合物,(η~5-Cp)_2Zr(OAr)2.(1,Ar=4-C_6H_5CH_2C_6H_4;2,Ar=3-CH_3-4-ClC_6H_3;3,Ar=3-NO_2C_6H_4;4,Ar=4-NO_2C_6H_4;5,Ar=3NH_2C_6H_4)同时对二氯二茂锆的环戊二烯基钠合成法加以改进,使产率由66%提高到81%.     

固体氩中一氧化氮的低温氧化

本文研究了在低温固体Ar中NO和O~2的反应。采用Ar作基质, 将NO和O~2分层沉积或混合沉积在低温基板上, 通过逐渐升温来控制扩散速率, 在温度10K-35K范围内, 从样品付里叶变换红外光谱的变化, 首次观察了NO和O~2反应中间体的生成和转化, 由此给出了反应机理, 即NO在Ar基质中首先发生扩散和聚合, 生成cis-(NO)~2, 随后与氧反应生成asym-N~2O~3和iso-N~2O~4, 而asym-N~2O~3进一步氧化生成N~2O~4(D~2~h)。     

Competitive coupling of amide anion over menthyl propionate anion with aryl radical

A competitive coupling of amide anion over menthyl propionate anion with aryl radicalin photo-S_(RN) 1 mechanism was encountered. The rcaction afforded N-aryl propionic amide in excel-lent yield. In contrast, the expected nucleophilic photo-S_(RN) 1 substitution originating from the carb-anion was observed in the case of t-butyl propionate. According to the proposed mechanisms and MOcorrelation diagrams of the coupling step of nucleophiles with aryl radical, the interesting con-trast is reasonably attributed to the variation in energy gap between π~*c-o and π~*Ar of (ArNu)-Usually, the odd electron of (ArNu)- is weightly populated at π~*c-o, however, the diminished priv-ilege of π~*c-o in menthyl propionate promotes a dominant population of the odd electron at π~*Ar,which leads to the fragmentation of (ArNu)- into the starting carbanion and aryl radical.     

菱形石墨炔薄膜He分离特性的密度泛函理论研究

氦气在科学和工业等领域中都具有不可替代的作用,其主要存在于天然气中。如何高效地从天然气中分离氦气显得至关重要。本文基于密度泛函理论(DFT)方法系统地探究了菱形石墨炔(rhombic-graphyne,R-GY)分离膜对He和其他天然气组分(Ne、Ar、CO_2、N_2和CH_4)的吸附、选择和渗透性能。结果表明,R-GY作为He分离膜可同时满足高选择性和高渗透率的要求。常温下,R-GY薄膜对He/Ne、He/CO_2、He/N_2、He/Ar和He/CH_4的选择性可分别达到2?10~7、3?10~(20)、9?10~(26)、7?10~(37)和5?10~(51),即使在600 K时仍可保持较高水平。此外,由于较低的扩散能垒,He穿透R-GY薄膜的渗透率在常温下可达到10~(-6) mol·m~(-2)·s~(-1)·Pa~(-1),高出工业标准近3个数量级;而其他气体组分在常温下的渗透率仅为10~(-58)-10~(-14) mol·m~(-2)·s~(-1)·Pa~(-1),气体无法渗透R-GY薄膜。     

四甲基二硅桥连双环戊二烯基四羰基二铁的芳香异腈取代及热重排反应

四甲基二硅桥连双环戊二烯基甲羰基二铁与芳香异腈在苯中加热回流生成一个 或两个羰基被芳香异腈取代的化合物（Me2SiSiMe2)(C5H4)2Fe2(CO)4-n(CNAr)n [Ar=C6H5,n=1(1),n=2(2);Ar=p-MeC6H4,n=1(3),n=2(4)]。单异腈取代化合物1和3 在二甲苯中加热均可发生热重排反应,生成相应的重排产物（Me2SiC5H4)2Fe2(CO) 3^-(CNAr)[Ar=C6H5(5),p-MeC6H4(6)]。通过^1H NMR,IR和元素分析表征了化合物 1－6的分子结构,并通过X射线衍射分析测定了化合物3的晶体结构。     

气体发生—MIPAES测定溶液中S^2—和SO3^2—的研究

用气体发生-MIPAES法测定了溶液中的S~(2-)和SO_(3)~(2-).样品中S~(2-)和SO_(3)~(2-)同稀H_2SO_4作用,产生H_2S和SO_2,用Ar气将产生的气体带入MIP.在216.9nm处测定硫的发射强度,考察了各实验参数对测定S~(2-)和SO_(3)~(2-)的影响.S~(2-)和SO_3~(2-)的检出限分别为0.08μg和0.25μg.RSD小于5％.     

过渡金属卡宾配合物:VIII. 四羰基[乙氧基(芳基)卡宾]铁配合物的方便合成法

五羰基铁, Fe(CO)~5(1), 与芳基锂(ArLi)在乙醚中于低温下反应, 所生成的酰羰基锂中间体在水溶液中于0℃用 Et~3OBF~4烷基化, 制得六个标题配合物(co)~4Fec(OC~1H~5)Ar(Ar:C~6H~5, 2;o-CH~3C~6H~4,3;p-CH~3C~6H~4, 4;p-CH~3OC~6H~4,5;C~6Cl~5,6;p-CF~3C~6H~4,7). 当用p-CF~3C~6H~4Li作为亲核试剂与1 反应时, 除生成7外, 还获得副产物对三氟甲基苯丙酮,p-CF~3C~6H~4COC~2H~5(8)。     

Tectonic setting discrimination and ~(40)Ar/~(39)Ar isotope geochronology of the Miba granite

The Miba granite is located in the juncture of Kang County in eastern Gansu Provinceand Lueyang County in Shanxi Province. It is considered to be the post-orogenic granite(POG-type) by major element discrimination method of Maniar. ~40Ar/~39Ar dating indicates that itsemplacement time is about 240-230 Ma and it is the result of the Indo-Sinian magmatism. In theearly Yanshan period (about 193.8 Ma), a thermal event resulted in the partial opening of the ar-gon isotope system of the biotite.     

过渡金属卡宾配合物:VIII. 四羰基[乙氧基(芳基)卡宾]铁配合物的方便合成法

五羰基铁, Fe(CO)~5(1), 与芳基锂(ArLi)在乙醚中于低温下反应, 所生成的酰羰基锂中间体在水溶液中于0℃用 Et~3OBF~4烷基化, 制得六个标题配合物(co)~4Fec(OC~1H~5)Ar(Ar:C~6H~5, 2;o-CH~3C~6H~4,3;p-CH~3C~6H~4, 4;p-CH~3OC~6H~4,5;C~6Cl~5,6;p-CF~3C~6H~4,7). 当用p-CF~3C~6H~4Li作为亲核试剂与1 反应时, 除生成7外, 还获得副产物对三氟甲基苯丙酮,p-CF~3C~6H~4COC~2H~5(8)。     

地震区温泉气体的地球化学特征

澜沧和巴塘地震区温泉气体的化学组成和He,Ar,CH_4(δ~(13)C)同位素组成的研究结果表明,He,H_2和非大气成因N_2的浓度以及~3He/~4He值与地震活动关系密切,地震活动过程中,气体的释放与岩石在应力作用下所呈现的力学特性——扩容性有关,两个地震区地震震级(能量)的对比研究表明,震级大,能量大,从岩石中气体释放量显著增加,温泉气体作为地震预报指标,下列参数更为有效:He,~3He/~4He,H_2和N_(2-B)/N_(2-总)。     

路易斯碱稳定的氢化硅亚胺:二胺基氯硅烷与氮杂环卡宾的反应性研究

硅亚胺作为亚胺的重元素类似物,是一类重要的含硅多重键化合物.本研究首次报道了氮杂环卡宾诱导下二胺基氯硅烷脱除Me3Si Cl来制备硅亚胺的方法.合成了二胺基氯硅烷[Ar N(Si Me_3)]_2SiHCl(2)(Ar=2,6-i-Pr_2C_6H_3),通过~1H NMR,~(13)C NMR,~(29)Si NMR,红外以及元素分析的表征确定了2的结构.研究了2与不同位阻氮杂环卡宾的反应性,发现其与位阻较大的1,3-二叔丁基咪唑-2-亚基(It Bu)和1,3-二异丙基-4,5-二甲基咪唑-2-亚基(Ii Pr)均不反应,但是其与位阻较小的1,3,4,5-四甲基咪唑-2-亚基(IMe_4)反应生成氢化硅亚胺3.     

Synthesis and Characterization of Organoboryl Germanium (Ⅱ) Oxides Containing Ge-O-B and Ge-O-B-O-Ge Cores

Organoboryl germanium(Ⅱ) oxides were synthesized from the 1,4-addition reaction of L'Ge(L'=HC[C(CH_2)N(Ar)]C(Me)N(Ar),Ar=2,6-iPr_2C_6H_3) with selected monosubstituted arylboronic acids RB(OH)_2(R=2,6-Me_2C_6H_3,2,4,6-Me_3C_6H_2,1-Naph) at the molar ratios of 1:1 and 2:1.The mononuclear products RB(OH)OGeL(L=CH[C(Me)N(Ar)]_2,Ar=2,6-iPr_2C_6H_3;R=2,6-Me_2C_6H_3(1),2,4,6-Me_3C_6H_2(2),1-Naph(3)) containing the Ge-O-B core were obtained smoothly through the 1:1 reaction.However,the reaction of L'Ge with 2,6-Me_2C_6H_3B(OH)_2 in a 2:1 ratio gave only the mononuclear product(1) instead of the expected binuclear one.What's more,a new borate compound [(2,6-Me_2C_6H_3)_4B_5O_6]~-[H:C]~+(4)(:C=C[N(iPr)C(Me)]_2) was concomitantly formed when the in situ prepared L'Ge was used as the precursor.In contrast,the use of 2,4,6-Me_3C_6H_2B(OH)_2 or1-NaphB(OH)_2 as the organoboryl source in the similar reaction led to the formation and isolation of the binuclear products RB(OGeL)2(R=2,4,6-Me_3C_6H_2(5),1-Naph(6)) containing the Ge-O-B-O-Ge core in a straight way.Compounds 1~6 were determined by single-crystal X-ray diffraction analysis.     

含烯烃配体的过渡金属卡宾配合物的研究 ⅩⅥ.丁二烯-和异戊二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物与三苯膦和亚磷酸三苯酯的反应研究

丁二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物,C_4H_6(CO)_2FeC(OC_2H_5)Ar(1,Ar=苯基,2,Ar=对甲苯基),在己烷溶液中于-60到-40℃与三苯膦或亚磷酸三苯酯反应生成产物3-6.当1与三苯膦在己烷中于60—70℃反应时,除了生成3外,还获得双膦配位的产物7.而异戊二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物与亚磷酸三苯酯反应则生成橙黄色结晶产物9,9的X射线衍射研究表明,二烯配体的键型发生了有趣的变化,即原铁配合物的π-烯丙基部分变为更有趣的含芳环的三烯体系和生成一个η~4配体以满足18电子规则.     

超音速流动条件下Sn/N_2O(O_2)化学发光反应动力学的实验研究

在温度低于900K 和1—10乇腔压范围内,首次采用等离子加热方法产生金属 Sn 蒸气,并利用超音速流动反应装置,研究了载气为 N_2和 N_2 Ar 时 Sn N_2O 和 Sn O_2的化学发光反应。首次采用光学多通道分析仪(OMA Model 1450)获得了不同腔压下 SnO(a~3∑~ ----X~1∑~ )跃迁的化学发光光谱,得出了不同腔压下 SnO(a~3∑~ )态的相对振动布居,并将本实验结果与低亚音速高温快速流动反应器(HTFFR)中所得的结果做了比较。