μ3-O-{[μ-(n-Bu)2Sn(μ-FcCO2)(n-Bu)2Sn]FcCO2}二聚物的晶体结构和分子结构

标题配合物Mr=933.84,属单斜晶系,空间群P2₁/n,晶胞参数a=15.244(4)Å,b=20.895(7)Å,c=12.375(4)Å,β=97.39(3)°,Z=4,V=3909(2)ų,Dc=1.5879·cm^-3,F(000)=1872,最终偏差因子R=0.0684.该配合物分子呈中心对称,是具有Sn₂O₂中心内环的二聚体,Sn₂     

Synthesis and structures of nickel(II) trimethylacetate dimers with coordinated diamines

Thermal decomposition of the tetranuclear nickel(II) complex Ni₄lη²-o-(NH₂)(NHPh)C₆H₄|₂(MeCN)₂(μ-OOCCMe₃)₄(η²-OOCCMe₃)₂ (I) under an inert atmosphere (o-xylene, 140 °C) was investigated. Under these conditions, the asymmetric binuclear complex Ni|η²-o-(NH₂)(NHPh)C₆H₄‖(η¹-o-(NH₂))(NHPh)C₆H₄|(η²,η-O,O-OOCCMe₃)(η²-OOCCMe₃) (2) was formed at the first stage. Complex2 was converted into the symmetric dimer Ni|η¹-o-(NH₂)(NHPh)C₆H₄|(μ-OOCCMe₃)₄ (3) upon recrystallization from benzene. The structures of complexes2 and3 were established by X-ray diffraction analysis. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1915–1918, November, 2000.     

二［氧合—二（4—二茂铁基苯甲酸二烷基锡（Ⅳ））］配合物？…

合成了｛［（ｎ－Ｂｕ）２Ｓｎ（４－Ｆｃ－Ｃ６Ｈ４ＣＯＯ）］２Ｏ｝２（１）和｛［ｎ－Ｏｃｔ）２Ｓｎ（４－Ｆｃ－Ｃ６Ｈ４ＣＯＯ）］２Ｏ｝２（２）（Ｆｃ＝ｆｅｒｒｏｅｎｙｌ两组新的配合物,对其进行了元素分析,并用ＩＲ,ＮＭＲ（＾１Ｈ,＾１３Ｃ,＾１１９Ｓｎ）进行了谱学表征,单晶Ｘ射线衍射法测定表明,配合物１的晶体属单斜晶系,Ｐ２１／ｃ空间群,晶胞参数ａ＝１．２９８８（１）ｎｍ,ｂ＝２．６５５（１）ｎｍ,     

二元羧酸取代的三核钼原子簇化合物的红外光谱与结构

本文考察了新合成的两个二元羧酸取代的三核钼衍生物Ｍｏ３Ｓ４（ＤＴＰ）３（ｐｈｔｈａｌａｔｅ）（Ｐｙ）（Ａ）（ＤＴＰ＝ｄｉｅｔｈｙｌ ｄｉｔｈｉｏｐｈｏｓｐｈａｔｅ,「Ｓ２Ｐ（ＯＥｔ）２」＾－）和Ｍｏ３Ｓ４（ＤＴＰ）３（ｍａｌｏｎａｔｅ）（Ｐｙ）（Ｂ）的红外吸收光谱,对Ｍｏ－Ｓ键及配体的主要吸收峰进行了归属和讨论,并与化合物Ｍｏ３Ｓ４（ＤＴＰ）４（Ｐｙ）（Ｃ）的谱图进行了比较。结果表明,通过对这类复     

Synthesis and Crystal Structure of a Binuclear Cobalt(Ⅱ) Carboxylate Complex Co_2(O_2CCMe_3)_4(C_9H_7N)_2①

１ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅＶａｎＮｉｅｋｅｒｋａｎｄＳｃｈｏｅｎｉｎｇ〔１〕ｆｉｒｓｔｄｅｍｏｎｓｔｒａｔｅｄｔｈｅｂｉｎｕｃｌｅａｒｎａｔｕｒｅｏｆｃｏｐｐｅｒ（Ⅱ）ａｃｅｔａｔｅｍｏｎｏｈｙｄｒａｔｅ,ｔｈｅｒｅｈａｓｂｅｅｎｃｏｎｓｉ...     

聚苯醚羧酸酯对C-PPO/PS共混体系的增容作用

前曾报道羧化度为8～lOmol%的羧化聚苯醚(C-PPO)与PS共混体系具有UCST和LCST共存的特殊相行为^[1],而羧化度大于11.6mol%时,C-PPO/PS共混体系表现出不相容性^[2,3]。化学改性PPO可作为PPO与其他聚合物共混的增容剂。本文讨论C-PPO的正十二酯(Lau-CPPO)对C-PPO/PO共混体系混溶性的影响。     

Quaternary ammonium ion dendrimers from methylation of poly(propylene imine)s

The poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈, DAB‐dendr‐(NH₂)₃₂, and DAB‐dendr‐(NH₂)₆₄ were fully converted with iodomethane to quaternary ammonium ions at both chain ends and branch points and, with less iodomethane, were partially converted to quaternary ammonium ions mainly at end groups. Amidation of the primary amine ends followed by treatment with iodomethane gave the first dendrimers with quaternary ammonium ions only at branch points. After an exchange of iodide counterions for chloride, all of the quaternary ammonium ion dendrimers slightly increased the rate of decarboxylation of 6‐nitrobenzisoxazole‐3‐carboxylate ion in an aqueous solution. Similar quaternary ammonium ion dendrimers with more hydrophobic interiors or more hydrophobic chains on the ends were much more active catalysts for the decarboxylation. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 821–832, 2001     

Darstellung carboxylatsubstituierter Rhenium-Gold-Metallatetrahedrane Re2(AuPPh3)2(μ-PCy2)(CO)7(η1-OC(R)O) (R = H,Me, CF3, Ph, 3,4-(OMe)2C6H3)

Synthesis of Carboxylate Substituted Rhenium Gold Metallatetrahedranes Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇(η¹-OC(R)O) (R = H, Me, CF₃, Ph, 3,4-(OMe)₂C₆H₃) The reaction of the in situ prepared salt Li[Re₂(μ-H)(μ-PCy₂)(CO)₇(ax-C(Ph)O)] ( 2 ) with 1,5 equivalents of monocarboxylic acid RCOOH (R = H ( 4 a ), Me ( 4 b ), CF₃ ( 4 c ), Ph ( 4 d ), 3,4-(OMe)₂C₆H₃ ( 4 e ) in tetrahydrofruan (THF) solution at 60 °C gives within 4 h under release of benzaldehyde (PhCHO) the η¹-carboxylate substituted dirhenium salt Li[Re₂(μ-H)(μ-PCy₂)(CO)₇(η¹-OC(R)O)] (R = H ( 4 a ), Me ( 4 b ), CF₃ ( 4 c ), Ph ( 4 d ), 3,4-(OMe)₂C₆H₃ ( 4 e )) in almost quantitative yield. The lower the pK_a value of the respective carboxylic acid the faster the reaction proceeds. It was only in the case of CF₃COOH possible to prove the formation of the hydroxycarbene complex Re₂(μ-H)(μ-PCy₂)(CO)₇(=C(Ph)OH) ( 5 ) prior to elimination of PhCHO. The new compounds 4 a–4 e were only characterized by ³¹P NMR and ν(CO) IR spectroscopy as they are only stable in solution. They are converted with two equivalents of BF₄AuPPh₃ at 0 °C in a so-called cluster expansion reaction into the heterometallic metallatetrahedrane complexes Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇(η¹-OC(R)O) (R = H ( 7 a ), Me ( 7 b ), CF₃ ( 7 c ), Ph ( 7 d ), 3,4-(OMe)₂C₆H₃ ( 7 e )) (yield 47–71% ). The expected precursor complexes of 7 a–7 e Li[Re₂(AuPPh₃)(μ-PCy₂)(CO)₇(η¹-OC(R)O] ( 8 ) were not detected by NMR and IR spectroscopy in the course of the reaction. Their existence was retrosynthetically proved by the reaction of 7 b with an excess of the chelating base TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-en) forming [(TBD)_xAuPPh₃][Re₂(AuPPh₃)(μ-PCy₂)(CO)₇(η¹-OC(Me)O] ( 8 b ) in solution. The η¹-bound carboxylate ligand in 7 a–7 e can photochemically be converted into a μ-bound ligand in Re₂(AuPPh₃)₂(μ-PCy₂)(μ-OC(R)O)(CO)₆ (R = H ( 9 a ), Me ( 9 b ), CF₃ ( 9 c ), Ph ( 9 d ), 3.4-(MeO)₂C₆H₃ ( 9 e )) under release of one equivalent CO. All isolated cluster complexes were characterized and identified by the following analytical methods: elementary analysis, NMR (¹H, ³¹P) spectroscopy, ν(CO) IR spectroscopy and in the case of 7 d and 9 b by X-ray structure analysis.     

锆簇基纳米分子胶囊的合成、晶体结构和荧光性质

选取4，4''-联苯二甲酸（4，4''-H₂BPDC）和2，6-萘二甲酸（2，6-H₂NDC）分别与二氯二茂锆（Cp₂ZrCl₂）反应制备了2例结构新颖的锆基纳米分子胶囊[Cp₃Zr₃（μ₃-O）（μ₂-OH）₃]₂（BPDC）₃Cl₂·H₂O（Zr-MC-1）和[Cp₃Zr₃（μ₃-O）（μ₂-OH）₃]₂（NDC）₃Cl₂·3H₂O（Zr-MC-2）。这2个分子胶囊均由3个线性羧基配体桥联2个三核茂锆建筑单元构成。利用单晶X射线衍射、粉末X射线衍射、元素分析、红外光谱、热重分析和氮气吸附-脱附等手段对化合物进行了表征。此外，荧光光谱分析表明Zr-MC-1和Zr-MC-2分别为深蓝光和蓝光发射材料，其最大发射波长分别为404和456 nm。     

以1,2,4,5-苯四甲酸或1,2,3,4-丁烷四羧酸为配体的金属有机框架的合成、表征及性质

以1,2,4,5-苯四甲酸(H_4BETA)与1,2,3,4-丁烷四羧酸(H_4BTCA)为有机配体,采用溶剂热法,成功合成了3个金属有机框架(Metal-Organic Frameworks,MOFs):{[Co_5(BETA)_2(OH)_2(H_2O)_2]·10H_2O}_n(1)、{[Zn_5(BETA)_2(OH)_2(H_2O)_2]·10H_2O}_n(2)和{[Mn_2(BTCA)(H_2O)_3]·H_2O}_n(3),并利用X射线单晶衍射、红外光谱(IR)、荧光光谱(PL)和热重分析(TG/DTG)等测试手段对其进行了表征。单晶结构研究表明3个MOFs均属于单斜晶系,P21/n空间群;框架1和2都是由1,2,4,5-苯四甲酸与五核的金属簇连接形成三维框架结构,沿a轴方向具有一维孔道结构,孔径大小为0.990 nm×1.307 nm;框架3是由1,2,3,4-丁烷四羧酸与Mn~(2+)连接形成4,8-c网络的三维框架结构。