系列异三核铬、锰、铁羧酸配合物的FAB-MS研究

进行了系列异三核羧酸配合物〔Ｍ２Ｍ＇Ｏ（Ｏ２ＣＲ）６Ｐｙ３ 〕Ｘ （Ｍ, Ｍ＇ ＝ Ｃｒ, Ｆｅ,Ｍｎ; Ｒ＝ Ｈ, ＣＨ３, Ｃ２Ｈ５, Ｐｙ＝ 吡啶; Ｘ ＝ Ｏ２ＣＨ, Ｏ２ＣＥｔ, Ｃｌ, ＣｌＯ４）的快原子轰击质谱（ＦＡＢ－ＭＳ）研究, 观察到异三核的２ 类重组反应： 第１ 类生成含有〔Ｍ３〕和〔Ｍ２Ｍ＇〕两种碎片离子, 第２ 类则生成含有〔Ｍ３〕, 〔Ｍ２Ｍ＇〕, 〔ＭＭ＇２〕和〔Ｍ＇３〕等４ 种不同组合的碎片离子。文中初步探讨了进行２ 类重组反应的原因和规律。根据所提出的规律确定了金属离子反应速率的顺序为Ｃｒ ＞ Ｆｅ ＞ Ｍｎ。     

夹心型钼磷酸盐的水热合成与晶体结构

采用水热法合成了首例含过渡金属铬的夹心型钼磷酸盐〔Ｈ３Ｎ（ＣＨ２）６ＮＨ３〕２Ｈ３｛Ｃｒ〔Ｍｏ６Ｏ１５（ＨＰＯ４）（Ｈ２ＰＯ４）３〕２｝·４Ｈ２Ｏ超分子化合物,用单晶Ｘ－射线测定其晶体结构,该晶体属三斜晶系,空间群Ｐ１。晶胞参数ａ＝１２．１５６（２）,ｂ＝１２．８０９（３）,ｃ＝１３．５３０（３）,α＝１０２．４６（３）°,β＝９３．６７（３）°,γ＝９３．４６（３）°．Ｖ＝２０４６．９（７）３,Ｚ＝１,Ｍｒ＝２７６８．６９,Ｄｃ＝２．２４６ｇ／ｃｍ３,Ｆ（０００）＝１３３７,μ＝２．１６２ｍｍ－１,全矩阵最小二乘法修正至Ｒ＝０．０６６６,ｗＲ＝０．１７４５,独立可观测点数为７１４２。化合物是分别由质子化的１,６－己二胺、水和｛Ｃｒ〔Ｍｏ６Ｏ１５（ＨＰＯ４）（Ｈ２ＰＯ４）３〕２｝７－阴离子构成,而｛Ｃｒ〔Ｍｏ６Ｏ１５（ＨＰＯ４）（Ｈ２ＰＯ４）３〕２｝７－是由２个〔Ｍｏ６Ｐ４〕与Ｃｒ３＋形成了６配位的夹心型阴离子     

三核过渡金属配合物〔M_3~ⅢO(OOCR)_6L_3〕 (M=Cr,Fe,Mn;R=CH_3,C_2H_5,CH_2NH_2;L=C_5H_5N,H_2O)的~1H NMR性质

采用１ＨＮＭＲ谱研究了通式为〔Ｍ３ⅢＯ（ＯＯＣＲ）６Ｌ３〕＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁交换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表明,其１Ｈ各向同性位移主要由接触作用贡献     

等瓣置换反应的研究——手性簇合物[η^—MeO2CC5H4）（CO）2Mo…

用Ｘ射线衍微法测定了由η＾５－ＭｅＯ２ＣＣ５Ｈ４（ＣＯ）３ＭｏＮａ和〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ－（ＣＯ）３Ｃｏ（ＣＯ）３（μ３－Ｓ）的等瓣置换反应所生成的手性簇合物－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｍｏ〕－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ（ＣＯ）３（μ３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数ａ＝０．８７１６２（５）ｎｍ，ｂ＝０．８     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２〕２／（μ－ＣＯ）２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

羰基铁－硫醇（硫酚）－格氏试剂体系与芳酰氯反应的研究──某些μ－芳酰基铁硫配合物的合成及结构

通过Ｆｅ３（ＣＯ）（１２）、硫醇（硫酚）和ＥｔＭｇＢｒ所形成的络盐［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］－Ｍｇ＋Ｂｒ与氯代芳酰氯的原位反应，合成了通式为（μ－ＲＳ）（μ－ｏ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６和（μ－ＲＳ）（μ－ｍ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６（Ｒ＝ｎ－Ｒｕ，ｔ－Ｂｕ，Ｐｈ）的６个新桥芳酰基铁硫配合物，并用Ｃ／Ｈ分析、ＩＲ和１ＨＮＭＲ表征了它们的结构。     

碳基铁—硫醇（硫酚）—格氏试剂体系与芳酰氯反应的研究：…

通过Ｆｅ３（ＣＯ）１２、硫醇（硫酚）和ＥｔＭｇＢｒ所形成的络盐［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ６）》－Ｍｇ＾＋Ｂｒ与氯代芳酰氯的原位反应，合成了通式为（μ－ＲＳ）（μ－ｏ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ６）和（μ－ＲＳ）（μ－ｍ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６（Ｒ＝ｎ－Ｂｕ，ｔ－Ｂｕ，Ｐｈ）的６个新桥芳酰基铁硫配合物，并用Ｃ／Ｈ分析、ＩＲ和＾１ＨＮＭＲ表征了它们的结构。     

三核过渡金属配合物[M3^ⅢO（OOCR）6L3]^＋（M=Cr,Fe,Mn;R=CH3,C2H5,CH …

采用＾１Ｈ ＮＭＲ谱研究了通式为（Ｍ３＾ⅢＯ（ＯＯＣＲ）６Ｌ３）＾＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其＾１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁变换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表     

环状配合物Me_2Si［η~5－C_5H_4Fe（CO）_2］_2SnR_2的合

通过ＳｎＣｌ_２对化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（Ⅰ）中Ｆｅ－Ｆｅ键的插入反应以及Ⅰ被Ｎａ－Ｈｇ齐还原所生成的相应双铁负离子｛Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２｝~（２－）与ＳｎＲ_２Ｃｌ_２（Ｒ＝Ｍｅ，Ｐｈ）的亲核反应，合成了环状化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２ＳｎＲ_２［Ｒ＝Ｃｌ（１），Ｍｅ（２），Ｐｈ（３）］。以元素分析、ＩＲ和~１ＨＮＭＲ谱表征了它们的结构，并用Ｘ射线衍射测定了配合物３的晶体结构。３为单斜晶系，空间群Ｐ２_１／ｎ，ａ＝１．０３８４（３）ｎｍ，ｂ＝１．６３８４（１）ｎｍ，ｃ＝１．５７６２（５）ｎｍ，β＝９７．９３（２）°，Ｖ＝２．６５６（２）ｎｍ~３，Ｚ＝４，Ｄｘ＝１．７１ｇ／ｍＬ。     

系列三核铬钒羧酸配合物的FAB-MS研究

进行了系列三核羧酸配合物 [M3O(O2 CCH3) 6(THF) 3]X (M3=Cr3,X =ClO4;M3=Cr2 V ,CrV2 ,V3,X =M Cl5(M 统计为 2 /3Cr+1 /3V) ,etc)的快原子轰击质谱 (FAB MS)研究 ,在V3和Cr3两个同三核配合物中 ,V配合物易脱RCO ,而Cr配合物更易脱RCO2 。在Cr2 V和CrV2 两个异三核配合物中观察到重组反应 :Cr2 V除 [Cr2 V]还生成含有 [Cr3]重组生成的碎片离子 ,CrV2 除 [CrV2 ]则生成含有 [Cr3],[Cr2 V],[V3]等其它三种重组碎片离子。充实了前文所探讨得重组原因和规律 ,根据重组反应 ,确定了金属离子反应速率顺序为Cr >V。根据所脱落的碎片 ,初步探讨了此类三核羧酸配合物催化羧酸脱羧成酮的机理。     

Synthesis, characterization and photophysics of a new series of anionic C,N,C cyclometalated platinum complexes

A novel series of anionic mononuclear terdentate dicyclometalated complexes (NBu4)[Pt(CwedgeNwedgeC)X] (HCwedgeNwedgeCH=2,6-diphenylpyridine) containing acetylide (X=C[triple bond]CR, R=tBu, 1; Ph, 2; Tol, 3; (4-OMe)C6H4, 4) or another anionic ligand (X=CN, 5; S-2Py, 6; CH2COCH3, 7) have been synthesized and fully characterized. The solid-state structures of complexes 1 and 4-6 have also been determined by X-ray diffraction studies, showing, in all the cases, the presence of several types of weak hydrogen interactions, leading to the generation of supramolecular 2D (1) or 3D (4-6) architectures. All the complexes (1-7) are intensely luminescent at low temperature (solid and glassy CH2Cl2), exhibiting concentration dependence in the emissions of the glassy CH2Cl2 matrix.     

三重桥氧三核铁脂肪酸配合物FAB和EI质谱研究

本文报道三重桥氧三核铁脂肪酸配合物[Fe_3(μ_3～O)(μ-O_2CR)_6(H_2O)]_3~+(R=CH_3,C_2H_5,C_3H_7,C_4H_9,C_(15)H_(31)和C_(17)H_(35))的快原子轰击(FAB)和电子轰击(EI)质谱。在FAB—MS谱中观察到四种系列离子:Ⅰ.[Fe_3O(O_2CR)_n]~+n=2-6;Ⅱ.[Fe_3O(O_2CR)_nO]~+n=1-4;Ⅲ.[Fe_2O(O_2CR)_n]~+n=1-3;Ⅳ.[Fe_2(O_2CR)_n]~+n=2-4;以及与底物所形成的加合离子[Fe_3O(O_2CR)_n·NBA-1]~+n=3-5(NBA是间-硝基苄醇)。在EI—MS谱中,除上述Ⅰ—Ⅳ离子(其中n的数目略有差异)外,还观察到含三个配位水的完整阳离子[Fe_3(O_2CR)_6(H_2O)_3]~+及其与配体羧酸的加合离子[Fe_3O(0_2CR)_n(H_20)_3·RCOOH+H]~+n=4-6,(Fe_3O(O_2CR)_nO(H_2O)3·RCOOH+H]~+n=2—4和Fe(O_2CR)_n]~+n=1—3。分析了它们的断裂规律,探讨了从中所获得的有益启示。     

Early-late heterobimetallic alkoxides as model systems for late-transition-metal catalysts supported on titania

Titanium complexes with chelating alkoxide ligands [TiCp*(O(2)Bz)(OBzOH)] (1) and [TiCp*(Me)((OCH(2))(2)Py)] (2) were synthesised by reaction of [TiCp*Me(3)] (Cp*=eta(5)-C(5)Me(5)) with 2-hydroxybenzyl alcohol ((HO)(2)Bz) and 2,6-pyridinedimethanol ((HOCH(2))(2)Py), respectively. Complex 1 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) to yield the early-late heterobimetallic complexes [TiCp*(O(2)Bz)(2)M(cod)] [M=Rh (3), Ir (4)]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O(2)Bz)(2)Rh(CO)(2)] (5). Compound 2 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) with protonolysis of a Tibond;Me bond to give [TiCp*((OCH(2))(2)Py)(mu-O)M(cod)] [M=Rh (6), Ir (7)]. The molecular structures of complexes 3, 5 and 7 were established by single-crystal X-ray diffraction studies.     

Synthesis and Crystal Structure of a Mixed－Valence Trinuclear Manganese Complex：Mn_3O（O_2CPh）_6（Py）_3

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆａＭｉｘｅｄ－ＶａｌｅｎｃｅＴｒｉｎｕｃｌｅａｒＭａｎｇａｎｅｓｅＣｏｍｐｌｅｘ：Ｍｎ_３Ｏ（Ｏ_２ＣＰｈ）_６（Ｐｙ）_３ＸｕＨａｏ；ＬｉＪｉｎ－Ｙｕ；ＬｉｕＱｉ；ＸｕＺｈｅｎｇ；ＹｏｕＸｉａ...     

Volatile imido-hydrazido compounds of the refractory metals niobium, tantalum, molybdenum, and tungsten

Volatile 1,1-dimethyl-2-(trimethylsilyl)hydrazido(1-) complexes of niobium, tantalum, molybdenum, and tungsten have been synthesized and fully characterized for use as precursors in their chemical vapor deposition to metal nitrides. Different reaction patterns were observed in the hydrazinolysis of imido complexes of those four metals with (trimethylsilyl)dimethylhydrazine HN(SiMe3)NMe2 (H-TDMH). [Ta(NtBu)Cl3Py2] gave [Ta(TDMH)2Cl3] (1) with loss of the imido functionality, and [M(NtBu)2Cl2Py2] gave [M(NtBu)2(TDMH)Cl] (M = W, 8a; Mo, 8b). Reactions of both types of metal imido complexes with magnesium hydrazides produced [M(NtBu)(TDMH)2X] (M = Ta, X = Cl, 2a; X = Br, 3a; M = Nb, X = Cl, 2b; X = Br, 3b) and [M(NtBu)2(TDMH)X] (M = W, X = Cl, 8a; X = Br, 9a; M = Mo, X = Cl, 8b; X = Br, 9b). Halogen substitution reactions at 2 and 3 by -NMe2, -NHtBu, and CH2Ph groups as well as imido ligand replacement reactions have been investigated. The results of crystal structure determinations of 1, 4a, 5a, 6a, 7b, and 9b are presented.     

Synthesis and Crystal Structure of K_8H_5［La（SiW_2Mo_9O_（39））_2（H_2O）_（17）］4H_2O

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＫ_８Ｈ_５［Ｌａ（ＳｉＷ_２Ｍｏ_９Ｏ_（３９））_２（Ｈ_２Ｏ）_（１７）］４Ｈ_２ＯＬｕＢｉｎ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＨａｒｂｉｎＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ，Ｈａｒ?..     

Tetraphosphinitoresorcinarene complexes: dynamic clusters with silver(I) and copper(I) halides

Silver(I) and copper(I) halide derivatives of several tetrakis(diphenylphosphinito)resorcinarene ligands are reported. The complexes [resorcinarene(O(2)CR)(4)(OPPh(2))(4)(M(5)X(5))], with resorcinarene = (PhCH(2)CH(2)CHC(6)H(2))(4), R = C(6)H(11), 4-C(6)H(4)Me, C(4)H(3)S, OCH(2)CCH, or OCH(2)Ph, M = Ag, X = Cl, Br, or I, M = Cu, and X = Cl or I, contain a crownlike [P(4)M(5)X(5)] metal halide cluster. These crown clusters were found to be dynamic in solution, as studied by variable-temperature NMR, and easily fragment to give the corresponding complexes containing [P(4)M(4)X(5)](-) and [P(4)M(2)(micro-X)](+) units. Reaction of pentasilver crown clusters with triflic acid gave the corresponding disilver complexes [resorcinarene(O(2)CR)(4)(OPPh(2))(4)]Ag(2)(micro-Cl)]]CF(3)SO(3). Thus, these resorcinarene-based ligands act as a platform for the easy and reversible assembly of copper(I) and silver(I) clusters with novel structures.     

Synthesis and Crystal Structure of a Tetranuclear Carboxylate-bridged Lanthanum(III)-Zinc(II) Complex [La_2Zn_2(m-CNC_6H_4COO)_(10)(Py)_2(C_2H_5OH)_2]

1 INTRODUCTION In the past few years, more extensive attention had been paid to the research on the chemistry of the heterometallic complexes containing simultaneously lanthanide (Ln) and transition metal ions[1～9]. Interest has been largely focused on the magnetic properties resulting from the Gd(III)-Cu(II) couple, which has been found to be directly ferromagnetic irrespective of the structural details[1～5]. Recent studies have further revealed that the magnitude of the ferromagnet…