meso—四（4—磺基苯基）卟啉（TPPS）及其锌配合物（ZnTPPS）的伏安法研究

本文用直流极谱法,循环伏安法研究了TPPS及其锌配合物ZnTPPS的极谱还原性质。实验表明TPPS的第一步电极反应为可逆的两电子还原过程,有两个H~ 参与反应。ZnTPPS第一步还原为不可逆电极过程,有一个H~ 参与。循环伏安图表明ZnTPPS还原时或还原后有Zn(Ⅱ)的还原,可能是ZnTPPS的离解所致。TPPS和ZnTPPS在汞电极有相近的强吸附作用。测算了吸附等温式,饱和吸附量,吸附分子的面积,吸附系数和吸附自由能等参数。     

四—[邻（叔丁氧羰甘氨酸）氨基苯基]卟啉锌配合物的合成 …

合成并表征了四－「邻（叔丁氨酸）氨基苯基」卟啉Ｈ２Ｔ（ｏ－ＢｏｃＧｌｙ）ＡＰＰ（１）及其锌（Ⅱ）配合物ＺｎＴ（ｏ－ＢｏｃＧｌｙ）ＡＰＰ（２）,用紫外－可光谱测定滴定法测定了配合物２与６种咪唑配体轴向配位反应的平衡常数,研究了它作为主体分子对咪唑类小分子的识别,研究结果表明,各配体的缔合常数按Ｋ（Ｉｍ）〉Ｋ（２－ＣＨ３Ｉｍ）〉Ｋ（ＫＭＩｍ）〉Ｋ（Ｎ－ＣＨ３Ｉｍ）〉Ｋ（２－ＨＯＣＨ２Ｉｍ）〉Ｋ（ＧＭＡ     

meso—四（4—氨基苯基）卟啉二阶导数光度法测定痕量锌

１引言用卟啉类显色剂测定痕量金属含量灵敏度很高，因而备受重视。但用导数光度法研究非水溶性卟啉显色剂的报道很少。非水溶性ｍｅｓｏ－四（４－氨基苯基）卟啉［Ｔ（４－ＡＰ）Ｐ］作为锌的显色剂研究尚未见报道。本文用二阶导数光度法建立了该卟琳测定痕量锌的新方法。该方法灵敏度高，选择性好，简便。用于测定水样中痕量锌，结果满意。２实验部分２．１主要仪器和试剂Ｂｅｃｋｍａｎ　ＤＵ－７Ｕ型分光光度计。锦标准溶液（用前稀释成１．００ｍｇ／Ｌ）；５．０×１０－４　ｍｏｌ／ＬＴ（４－ＡＰ）Ｐ的ＤＭＦ溶液。２．２实验方法…     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

PHOTOLYSIS OF AQUEOUS SOLUTIONS OF POTASSIUM CIS-DIAQUOBIS (OXALATO) CHROMATE (III)

Abstract— The photolysis of aqueous solutions of cis -[Cr(C₂O₄)₂(H₂O)₂]- at 254 nm and pH 4 produced CO₂ and H₂ in nearly equal yields. The quantum yield of hydrogen, φ², increased by 9% and the yield of carbon dioxide, φ, by 65% as the pH was lowered from 4 to I. The total gas yield, φ_gas, decreased in the presence of added oxalate or chromium (II) ions and when the light intensity was lowered. The gas yield in D₂O was appreciably higher than in H₂O. The variation of φ_gas with pH (D) and with added oxalate ion was roughly parallel in the two liquid media. The gas yield increased in the series:
A tentative mechanism is suggested to explain the results.     

MOLECULAR STRUCTURE OF (BENZOPHENONE)BIS(TRICARBONYLCHROMIUM)

<正> The title crystal belongs to monoclinic system, space group P21/c, with 3=14.794(2), b=7.360(1), c=16.029(2) A, β=94.95(2)0, Z=4, V=1738.9(6)A3, Dx=1.735 g/cm3. The final R=0.047, Rw=0.052.     

INFRARED ASSIGNMENT OF BIS(GLYCOLATO)-BIS(PYRIDINE) METAL(II) COMPOUNDS AND CRYSTAL STRUCTURE OF TRANS-BIS(GLYCOLATO)-CIS-BIS(PYRIDINE)NICKEL(II) DIHYDRATE

Abstract

Infrared spectra of the coordination compounds [MG₂(py)₂], M(II)=Co, Ni, Cu and Zn; G=glycolato, py=pyridine, have been fully assigned by means of py and py-d ₅ and glycolato α—OH and α—OD (G-d) labelling as well as metal ion substitution in the 4000–70cm^?1 region. The crystal structure of the Ni(II) compound is presented and the spectra of the compounds are discussed on the basis of their structure and their bonding to the glycolato and pyridine ligands. Vibrational frequencies obtained for the Ni(II) compound are compared to those obtained by calculations carried out using the Gaussian 94 program package.     

三(对-甲苯磺酰氧甲基)硝基甲烷的还原和N-三(对-甲苯磺酰氧甲基)甲基羟氨的空气氧化

三(对-甲苯磺酰氧甲基)硝基甲烷(1)于苯中,以锌粉和醋酸在加或不加醋酸酐下可以被还原,并分別形成相应的羟氨(2)或其醋酸酯(3)。值得注意的是,当2和3以1M甲醇钠在氯仿中处理时,受空气氧化后又形成硝基化合物(1),但在排除空气时,不发生这一氧化反应。同样,三(苯甲酰氧甲基)硝基甲烷当用锌粉-醋酸还原时可生成相应的胺。     

KINETICS OF THE CHROMIUM(II) REDUCTIONS OF CHELATED AMINO ACIDO-BIS(ETHYLENE-DIAMINE)COBALT(III) COMPLEXES

Abstract

The kinetics of Cr²⁺(aq) reductions of glycinato-, D,L-alanato, D,L-phenylalanato-, and D,L-leucinatobis-(ethylenediamine)cobalt(III) ions have been investigated. The rate law is of the form d(ln[Co(III)]/dt = k[Cr²⁺], where the rate constant k(M^?1sec^?1) and associated activation parameters δH^δ(kcal mol^?1 and δS^δ (cal deg ^?1mol^?1) in parentheses, are respectively 1.65 · 0.06 (9.7 · 0.1, -25 · 1), 0.367 · 0.008 (10.9 · 04,-24 ·1), 0.529 · 0.021 (11.2 · 0.4, -22 · 1); and 0.358 · 0.019 (11.5 · 0.3, -22 · 1) at 298^·K and ·[CIO·] = 1.0 M. The reactions are all inner-sphere.     

四(邻N-甲基烟酰胺基)苯卟啉与Cu(Ⅱ)的反应动力学研究

在20.0±0.1℃,0.1M KCl介质及乙酸或丁二酸缓冲条件下,研究了水溶性的四(邻N—甲基烟酰胺基)苯卟啉(H_2-TM(O-Nic)PP)与Cu(Ⅱ)的反应动力学。实验结果表明,Cu(Ⅱ)嵌入H_2-TM(O-Nic)PP的反应速率对卟啉是一级反应。表观一级速率常数表达式如下:对Cu(Ⅱ)-酸盐体系,其中,对Cu(Ⅱ)-丁二酸盐体系,其中,提出了Cu(Ⅱ)嵌入H_2-TM(O-Nic)PP的反应机理,并对乙酸缓冲体系和丁二酸缓冲体系中反应动力学的差别作出了讨论。     

STRUCTURES OF PYRIDINE CARBOXYLATE COMPLEXES OF COBALT(II) AND COPPER(II)

Abstract

The syntheses and crystal structures of [Co(nic)₂(H₂O)₄] (1). [Co(iso)₂(H₂O)₄] (2). [Cu(nic)₂(H₂O)₄] (3), and [Cu(iso)₂(H₂O)₄] (4) (nic = nicotinate; iso = isonicotinate) are reported. Complex 1 crystallizes in monoclinic, space group C2/m with cell parameters a =14.150(4). b = 6.883(2)., c = 8.497(2) Å, β= 118.28(2)° and Z = 2. The other crystals. 2. 3. and 4. are all triclinic, Pī; a = 9.777(3), b = 6.348(4), c = 6.888(3)Å, a= 113.10(6)., β= 110.55(3). γ = 97.61(5)°, and Z=l for 2; a = 7.0281(4), b = 7.7176(6), c = 8.6978(7)Å, a = 68.103(7), β = 68.526(5), γ = 62.550(6)°, and Z=1 for 3; a = 9.1807(4), b = 6.3334(3), c = 6.8871(3)Å, a= 108.213(4), β = 99.433(4), γ= 105.190(4)°, and Z= 1 for 4. The arrangements around the metal ions are trans-octahedra with two pyridyl nitrogens and two aqua oxygens in the equatorial positions and two aqua oxygens in the axial positions, although the Cu(II) complexes show a larger Jahn-Teller distortion.     

STEREOCHEMISTRY OF (R)-2-METHYLAZIRIDINE COMPLEXES OF COBALT(III) AND DIMERIZATION OF THE LIGAND

Abstract

A cobalt(III) complex containing (R)-2-methylaziridine (R-meaz), [Co(R-meaz)(NH₃)₅]³⁺, was prepared and the two diastereomers arising from the presence of the chiral nitrogen atom (N(R) and N(S)) were separated by column chromatography. Molecular mechanics calculations estimated the N(R)-isomer to be more stable. This result was supported by the x-ray structure determination of the more abundant (ca. 94%) isomer, N(R)-[Co(R-meaz)(NH₃)₅]Br₃H₂O. Crystal data: monoclinic, P2₁, a = 7.357(1), b = 9.780(1), c = 10.426(1) Å, μ = 93.58(1)°, V= 748.7(3) ų, Z= 2. Kinetic studies of isomerization (epimerization) between the two isomers revealed that inversion at the nitrogen center was very slow (5 × 10^?2 M^?1 S^?1at 25 °C). The small rate constant seems to be related to the strained three-membered structure of the meaz ligand. The reaction of Na₃[Co(N0₂)6] and R-meaz yielded a complex containing two dimerized R-meaz chelates, trans-[Co(NO₂)2(di-R-meaz)₂] (di-R-meaz =RR)-α,2-dimethyl-l-aziridineethanamine). The crystal strucrure of trans-[Co(NO₂)₂ (di-R-meaz)₂]C1O₄H₂O was established by x-ray crystallography. Crystal data: orthorhombic, P2₁2₁2₁, a = 11.784(6), b = 21.023(9), c = 8.608(7) Å, V = 2133(2) ų, Z = 4.     

丙烯酸甲酯与N-对卤苯基甲基丙烯酰胺共聚合的研究

<正> 我们已经报道过甲基丙烯酸甲酯与N-对卤苯基甲基丙烯酰胺共聚合的研究。本文工作合成了丙烯酸甲酯与N-对卤苯基甲基丙烯酰胺共聚体,研究了这二组共聚体系的聚合反应、共聚体的组成、估算了单体的竞聚率,比较了这两种酰胺对丙烯酸甲酯与甲基丙烯酸甲酯的反应活性。