Synthesis and physico-chemical properties of diruthenium(III, II) tetra-aryl carboxylato compounds

Monochloro-tetra-μ-aryl-carboxylatodiruthenium(III, II) compounds Ru2Cl (O2CAr)4 (Ar = -C6H5; -C6H4-p-OCH3), are prepared and characterized. The compounds have magnetic moments that correspond to three unpaired spins per dimer. The Rusingle bondRu bond order is 2.5 and the ground electronic configuration is σ2π4δ2(δ*π*)3. The visible spectral band is observed at ca 450 nm along with a shoulder near 580 nm in DMF solution. The compounds undergo a one-electron Ru(III)Ru(II) → Ru(II)Ru(II) quasi-reversible reduction in DMF near 0.0 V vs sce.

稀土(III)及铜(II)、锌(II)有机磷（膦）酸酯配合物的晶体结构和振动光谱研究

本文包括标题配合物的结构和振动光谱两部分，共涉及了M(DMP)_n {n=2.3, M=2a, Nd, Cu. Zn}, Ln(DPP)_3{2n=2a-2u, Y}和Ln(BBP)_3 {Ln=La-Lu. Y}三类三十四个配合物。在结构方面，首次测定了Zn(DMP)_2和Cu(DMP)_2呈现出链状配位高聚结构，而La(DMP)_3, La(DMP)_3则为平面网状配位高聚结构。在Zn(DMP)_2, La(DMP)_3和Nd(DMP)_3中，配体以对称“O－P－O”桥键与金属原子配位，在相邻金属原子间形成双桥键。在Zn(DMP)_2中，每个Zn原子通过“O－P－O”双桥键与另两个Zn原子连接，Zn原子配位数为4，配位多面体为四面体构型；在La(DMP)_3和Nd(DMP)_3中，每个稀土原子通过“O－P－O”双桥键与另外三个稀土原子相连接，稀土原子的配位数为6，配位多面体LnO_6为八面体构型。在Cu(DMP)_3中， 配体以对称和非对称“O－P－O”桥键两种形式存在，其中非对称配位的配体形成为“Cu-O-P_O-Cu"-Cu，在铜原之间形成了一个单氧桥键。每个Cu原子通过双“O－P－O”桥键以及双单氧原子桥键与另外三个Cu原子相连接，Cu原子配位数为5，配位多面体为四角锥构型。在振动光谱方面，得到了上述配合物较为完整的光谱数据，并对主要光谱带进行了归属，如V_(M-O), V_(PO_2), V_(P-O(c)),VC-O, VP-C及σ_PO_2等。在稀土配合物中，稀土配位键的伸缩振动V_(vn-o)位于250cm~(-1)附近。V_(Cu)和V_(Zn-o)，在Cu(DMP)_2和Zn(DMP)_2中，分别为(412cm~(-1), 370cm~(-1))和(393cm~(-1), 386cm~(-1))。V_(as)PO_2和V_sPO_2，在配合物振动光谱中，分别在1130－1249cm~(-1)区和1084－1156cm~(-1)区。在稀土配合物中，VL_(n-o), V_(as)PO_2频率值，随镧系收缩逐渐递增。在Cu(DMP)_2红外谱中，非对称配体和对称配体的V_(as)PO_2和V_sPO_2, 分别为(1249cm~(-1)，1156cm~(-1))及(1177cm~(-1)，1090cm~(-1))，其劈裂值△V(V_(as)PO_2-V_sPO_2)为93cm~(-1)和87cm~(-1)。通过对配合物的常温和低温红外光谱的比较，确认了La(DMP)3和Nd(DMP)_3的176cm~(-1)、Ln(DPP)_3和Ln(BBP)_3的150cm~(-1)附近吸收为晶格振动。Ln(DPP)_3、Ln(BBP_3)的光谱性质与Ln(DMP)_3相似，我们认为它们之间具有相同的骨架结构－平面网状配位高聚结构。

Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.

Two pentacoordinate copper(II) complexes that display accessible Cu(III/II) couples

Two copper(II) complexes of the type CuL2.imidazole (1) and Cu2L4(4.4'-bpy).2H(2)O.C6H14 (2), where LH = 1-nitroso-2-naphthol and 4.4'-bpy = 4,4'-bipyridine, are characterised by X-ray crystallography. In 2, the two copper atoms are linked by 4,4'-bpy. In both the complexes, copper is found to have a distorted square pyramidal N3O2 coordination sphere. The axial position in I is occupied by an oxygen atom while those in 2 by the nitrogen atoms of 4.4'-bpy. The two complexes display quasireversible Cu(III/II) couples around 0.68 V vs. saturated calomel electrode in cyclic voltammetry in dichloromethane.

D. Danielis Ludouici, ... Opera omnia : et quidem I. De pharmacia moderno secula applicanda Dissertationes III, II De vollatilitate salis Tartari dissertatio, III De morbis castrensibus & dysenteria tractatus duo, nunc primum a Germanico idiomate ... in Latinum translati : IV Obseruationes physico-chimico-medicae curiosae XLVIII ... /

Mode of access: Internet.

Dinuclear cyano-bridged Co-III-Fe-II complexes as precursors for molecular mixed-valence complexes of higher nuclearity

The preparation and characterization of a series of trinuclear mixed-valence cyano-bridged Co-III-Fe-II-Co-III compounds derived from known dinuclear [{LnCoIII(mu-NC)}Fe-II(CN)(5)](-) complexes (L-n = N-5 or N3S2 n-membered pendant amine macrocycle) are presented. All of the new trinuclear complexes were fully characterized spectroscopically (UV-vis, IR, and C-13 NMR). Complexes exhibiting a trans and cis arrangement of the Co-Fe-Co units around the [Fe(CN)(6)](4-) center are described (i.e., cis/trans-[{LnCoIII(mu-NC)}(2)Fe-II(CN)(4)](2+)), and some of their structures are determined by X-ray crystallography. Electrochemical experiments revealed an expected anodic shift of the Fe-III/II redox potential upon addition of a tripositively charged {(CoLn)-L-III} moiety. The Co-III/II redox potentials do not change greatly from the di- to the trinuclear complex, but rather behave in a fully independent and noncooperative way. In this respect, the energies and extinction coefficients of the MMCT bands agree with the formal existence of two mixed-valence Fe-II-CN-Co-III units per molecule. Solvatochromic experiments also indicated that the MMCT band of these compounds behaves as expected for a class II mixed-valence complex. Nevertheless, its extinction coefficient is dramatically increased upon increasing the solvent donor number.

Vetus Testamentum, pars II.

Avec prologues et « capitula ». Reg. II,VII,22-XI,14 (2), III,II,46-VIII,29 (5), II,XIX,12-III,II,41 (13), II,VI,19-VII,22 (29), II,XIV,9-XVIII,24 (30), II,XII,10-XIII,5 (36), III,VIII, 30-XXII,54 (37), IV,I,1-XXV,30 (61) ; Job (98v) ; Tobias (120).

Recueils de pièces concernant les règnes de Henri III, Henri IV, Louis XIII et Louis XIV. (1582-1644).

Contient : I Registre des sept dernières années du règne de Henri III ; II Pièces diverses, concernant les règnes de Henri III, Henri IV, Louis XIII et Louis XIV. (1586-1644)

Spectroscopic and electrochemical properties of iron(II) complexes of polydentate Schiff bases containing pyrazine, pyridine and imidazole groups

We report the synthesis and spectroscopic/electrochemical properties of iron(II) complexes of polydentate Schiff bases generated from 2-acetylpyridine and 1,3-diaminopropane, acetylpyrazine and 1,3-diaminopropane, and from 2-acetylpyridine and L-histidine. The complexes exhibit bis(diimine)iron(II) chromophores in association with pyrazine, pyridine or imidazole groups displaying contrasting pi-acceptor properties. In spite of their open geometry, their properties are much closer to those of macrocyclic tetraimineiron(II) complexes. An electrochemical/spectroscopic correlation between E degrees(Fe(III/II)) and the energies of the lowest MLCT band has been observed, reflecting the stabilization of the HOMO levels as a consequence of the increasing backbonding effects in the series of compounds. Mossbauer data have also confirmed the similarities in their electronic structure, as deduced from the spectroscopic and theoretical data. (C) 2008 Elsevier B.V. All rights reserved.

Libri de re rustica : M. Catonis, lib. I. M. Terentii Varronis lib. III. L. Iunii Moderati Columellae lib. XII. Eiusdem de arboribus liber separatus ab alijs ... Palladii lib. XIIII. De duobus dierum generibus simulq[ue] de vmbris [et] horis quae apud Pal

Lugares e imp. tomados de Short-title catalogue of books printed in the German-speaking countries and German Books printed in other countries from 1455 to 1600 now in the British Museum

Libri de re rustica : M. Catonis, lib. I. M. Terentii Varronis lib. III. L. Iunii Moderati Columellae lib. XII. Eiusdem de arboribus liber separatus ab alijs ... Palladii lib. XIIII. De duobus dierum generibus simulq[ue] de vmbris [et] horis quae apud Pal

Lugares e imp. tomados de Short-title catalogue of books printed in the German-speaking countries and German Books printed in other countries from 1455 to 1600 now in the British Museum

Infrared spectroscopic study of the phase transitions in CsNO3, RbNO3 and NH4NO3

Phase transitions of CsNO3 (II-I), RbNO3 (IV-III-II) and NH4NO3 (V-IV-III-II-I) have been studied by i.r. spectroscopy. The study has provided useful information on the changes in the dispositions of the ions during the phase transitions.

北京市郊区可持续景观生态规划及 优化生态生产范式研究——以昌平区为例

北京市郊区可持续景观生态规划及优化生态生产范式研究是指要遵循区域自然地理要素的分异规律，以土地利用现状格局为基础，以景观生态学原理和可持续发展准则为理论指导，以景观空间分析为具体研究内容来揭示区域土地利用类型结构、功能的异质性和有序性，以期提出优化的土地利用格局。本论文主要通过大量数据、图件的收集、野外考察与调查，文献查阅与数据处理、分析，得出以下主要结论： 一、理论方面 基于景观生态学理论——景观要素，空间结构与生态学过程，景观动态，异质性，等级结构，连接度以及景观的时空性等，以北京地区为例阐述了景观生态学理论如何合理地整合于生态建设与保育之中，并重点阐释了北京生态建设与保育“小三圈”格局的结构与功能，该系统包括山区外圈层、郊区平原中圈层和城区内圈层，其目标要实现：(1)山区发挥以水源涵养、水土保持防护为主的生态功能;(2)郊区创建农田、林地、草地异质性的人工稀树草原景观，形成带、网、片、点相结合的绿网系统;(3)城区以自身绿化和美化为主。同时，本研究针对我国的区域可持续发展进一步提出更加有效的建设性意见：(1)开展区域生态适宜性评价;(2)区域水平的土地利用格局、动态以及预测性研究;(3)进行区域可持续景观生态规划，建立区域优化生态生产范式，最终实现可持续发展目标。 二、研究方法方面 利用空间自相关指数，并结合“城-郊-乡”梯度分析法研究景观格局对尺度（包括粒度、幅度、方向）变化的响应。得出以下主要结论： 1、景观格局对于尺度变化有着不同的响应，随着空间粒度的增加，空间自相关均呈下降趋势;随着幅度的增加，空间自相关基本不变;人类干扰较多的景观几乎不受“划区效应”的影响;不同的数据类型，同一数据类型的不同景观对于尺度的变化均有着不同的响应。 2、沿“城-郊-乡”样带，空间自相关呈阶梯状增加趋势。景观空间自相关大小顺序：林牧景观>林果景观>农田景观>都市景观>都市化景观，人为干扰较多的景观具有较低的空间自相关，但对尺度的变化表现出较强的敏感性。 三、实例研究 北京市郊区可持续景观生态规划及优化生态生产范式研究是以昌平区为例，从昌平区经济与产业结构现状分析出发、以昌平区土壤理化性状分析为背景，以景观格局现状、动态，以及土地利用内部转移格局与过程、驱动因素分析为主要内容，并且重点探讨了昌平区城镇化的过程特征及空间特征，得出以下主要结论： 1、昌平区GDP配比方式，以及昌平区农村GDP结构模式均为“三二一”。昌平区在北京市农业中的地位，以及农业在昌平区GDP中所处地位均弱化。截止2001年，昌平区农业产值中，牧业>种植业>渔业>林业，牧业居于首位，占到46.70%，而传统种植业也正以小汤山为龙头向现代化、高科技、高效化的“六种农业”转化。总体讲，农业的粮食生产功能在昌平区已不再是一个重要功能，传统种植业正逐步地让位于畜牧业（人工牧草）、林业（疏林、苗圃），突出体现了具有良好生态学效益的牧草、林果在未来大农业发展中的战略地位。 2、昌平土壤肥力状况良好，景观分区与土壤理化性质是吻合的。基于土壤理化基质，昌平区应形成林、灌、草为主的山区景观，园林式城镇、林、果、灌相结合的山前倾斜平原景观，以及农、林、草配置的生态农业景观和花卉、种苗、绿化带相辉映的绿色生态住宅景观。 3、从1989~2001年期间，研究区内土地利用景观经历了很大的变化。土地利用景观的量变主要体现在城镇用地的迅速扩张和耕地的锐减，而土地利用类型的变化则体现在水田、传统菜地的逐渐消失，以及2001年后人工牧草的大面积推广种植。景观格局在不同景观分区的差异也得以论证，中北部山麓平原卫星城镇、旅游林果区（III）具有最高的多样性和最低的优势度、聚集度，中南部平原高科技、都市生态农业区（II）的多样性最低，而优势度、聚集度最高，对于南部平原都市边缘、城镇住宅区（I）各指标则介于III和II区之间。 4、从1989~2001年期间，土地利用的内部转移主要体现在耕地向城镇用地的大面积转移，其次，传统菜地转向城镇用地和其他种植耕地，而人工牧草是由部分耕地转移而来的。城镇化、水资源短缺和农业政策是主要驱动因素。土地利用的内部转移具有明显的区域差异，中北部山麓平原卫星城、旅游林果区体现出卫星城镇的发展，南部平原都市边缘住宅区则反映出北京都市边缘的向外扩张，而中南部平原高科技都市农业区则正向现代化的、高科技都市农业示范区发展。 5、昌平区三种主要的城镇化模式，即都市边缘带状城镇扩展模式、交通主轴线状城镇扩展模式和卫星城面状城镇扩展模式。研究表明，昌平区的城镇化主要集中在1989~1996年期间。 基于昌平区的产业与经济结构现状，土壤养分状况，景观结构现状、动态，土地利用转移方向，并且结合昌平区自然地理分异规律，社会经济因素对昌平区进行了可持续景观规划，昌平区应遵循的四个景观分区为：北部中低山生态保护、生态旅游区;中北部山麓平原卫星城镇、旅游林果区;中南部平原高科技、都市生态农业区;南部平原都市边缘、城镇住宅区。 最后作为总结、归纳，我们提出昌平区优化生态生产范式，昌平区的发展应定位于（1）生态环境保护与水源涵养的生态功能;（2）教育、示范、创新功能;（3）生活功能，并且遵循自然地域分异规律原则、因地制宜原则、生态主导性原则、统筹兼顾原则，大力发展昌平区经济的优势产业，即畜牧业、林果业和旅游业，突出肉羊、苹果、牧草和林木种苗等四个具有昌平特色的主导产业。 景观生态学;景观空间格局;可持续景观生态规划;土地利用变化;优化生态生产范式;北京昌平区