二元羧酸二(二茂镱)的合成

本文报道了五个新的二元羧酸二(二茂镱)的合成:(COO)_2Yb_2(C_5H_5)_4(1),CH_2(COO)_2Yb_2(C_5H_5)_4(2),(CH_2COO)_2Yb_2(C_5H_5)_4(3),o-C_6H_4(COO)_2Yb_2(C_5H_5)_4(4),p-C_6H_4(COO)_2Yb_2(C_5H_5)_4(5),并考察了它们对空气的稳定性。     

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%.     

过渡金属氢化物和聚集双键化合物反应的研究——Ⅳ.Cp_2Zr(H)Cl、(Cp_2ZrH_2)_x与RNCO(R=C_6H_5,α-C_(10)H_7)的反应

本文报道了二茂锆氢化物与异氰酸酯在不同条件下的反应。Cp_2Zr(H)Cl与RNCO(R=C_6H_5,α-C_(10)H_7)在苯中,5～10℃下反应,生成锆的氧桥络合物(Cp_2ZrCl)_2O(1)和Schiff碱型化合物RN=CH_2(2:R=C_6H_5;3:R=α-C_(10)H_7)。当反应在25～30℃下进行时,还有少量有机胺RNH(CH_3)及很少量的RNHCONHR生成。而(Cp_2ZrH_2)_(?)与RNCO反应时,同时发生加成和脱氧两种反应,生成双齿配位络合物Cp_2Zr(H)[RN=C(H)=O](4:R=C_6H_5;5:R=α-C_(10)H_7)和化合物(Cp_2ZrO)_3(6)、RNH.(CH_3)(7:R=C_6H_5;8:R=α-C_(10)H_7)及少量未知化合物。产物经元素分析、IR、~1H及~(13)C NMR和GC-Ms谱分析鉴定。     

铁双(环戊二烯巯基)环戊二烯基钛(Ⅳ),锆(Ⅳ)的合成和结构表征

1,1’-二巯基二茂铁分别和二氯二茂钛(Ⅳ),二氯二茂锆(Ⅳ)在无水苯中在氨基钠存在下反应,合成了两个未见报道的化合物Fe(η~5-C_5H_4S)_2M(η~5-C_5H_5)Cl[M=Ti,Zr]。它们的组成和结构经元素分析,IR和~1HNMR得到证实。     

一茂二元羧酸镱的合成

本文报道了五个新的一茂二元羧酸镱的合成:o-C_6H_4(COO)_2YbC_5H_5(1),(CH_2COO)_2YbC_5H_5(2),(CHCOO)_2YbC_5H_5(3),CH_3(COO)_2YbC_5H_5(4),(COO)_2YbC_5H_5(5),这些络合物均经元素分析和红外光谱鉴定。可能由于这些络合物具有螯合环的结构,所以它们在空气中的隐定性较强。     

STUDY ON THE STRUCTURES OF COORDINATION COMPOUNDS OF N-(ortho-METHYL)-AND N-(ortho-METHOXY)-PHENYL IMINODIACETATO-Cu(Ⅱ)

The coordination compounds,{Cu[CH_3C_6H_4N(CH_2COO)_2]}.2H_2O and{Cu[CH_3OC_6H_4N(CH_2COO)_2]}.2H_2O,have been prepared and its crystal struc-tures determined.The final discrepancy factors are R=0.052,R_w=0.061 for(I)and R=0.052,R_w=0.039 for(Ⅱ).The geometry of the coordination poly-hedron with Cu(Ⅱ)is a distorted tetragonal pyramid for(Ⅰ)and an unsym-metrical and extended tetragonal bipyramid for(Ⅱ),respectively.The re-sults of EHMO calculations indicate that the ligand mainly provided thefield with very few of its electrons being coordinated to the central atom.     

二茂铁衍生物的合成、表征及猝灭Ru(bpy)_3~(2+)发光的研究

本文以邻菲罗啉和二茂铁为原料,合成了一系列新Schiff碱型二茂铁衍生物:(C_(10)H_6N_2)C=N—N=CR—Fe,(C_(10)H_6N_2)C=N—C_6H_4—N=CR—Fe,(C_(10)H_6N_2)C=N—C_6H_4—C_6H_4—N=CR—Fe,(R=H,CH_3,Fe为二茂铁基);并对其进行了元素分析和光谱表征.该类二茂铁衍生物能有效地猝灭Ru(bPY)_3~(2+)的发光,Stern-Volmer图呈线性关系,双分子猝灭过程速率常数k_q为10(?)dm~3/mol·s~(-1)数量级.猝灭过程按电子转移还原机理进行.     

二甲基-2'-乙酰基双二茂铁甲烷的晶体和分子结构

二甲基-2′-乙酰基双二茂铁甲烷C_5H_5FeC_5H_4C(CH_3)_2C_5H_4FeC_5H_4COCH_3为深紫色菱形晶体,m.p.115.5～116.5℃。它属单斜晶系,P2_1/c空间群。晶胞参数为:a=11.626(1),b=13.219(1),c=13.078(2)A,β=90.67(1),V=2009.8A~3,Z=4,Dc=1.501g/cm~3。用MULTAN-78直接法程序求解晶体结构,最后偏离因子R=0.040。中心C原子周围的四个基团以变形四面体取向,分子本身不具有任何对称性。     

铂氢化物的研究——Ⅱ.新铂氢化物PtH(PPh_3)(S_2CNR_2~1)及trans-PtH(PCy_3)_2(S_2CNR_2~1)的合成与结构鉴定

trans-PtHX(PR_3)_2(X=卤素,R=烃基)型氢化物中与氢对位的配体可被其它配体如CN~-,SCN~-及中性分子等取代,生成各种氢化物。我们研究了trans-PtHCl(PR_3)_2[R=苯基,环己基(Cy)]与二硫代胺基甲酸钠盐NaS_2CNR_2~1(R~1=C_2H_5,n-C_4H_9,C_6H_5CH_2)的反应,得到两类新的氢化物PtH(PPh_3)(S_2CNR_2~1)(1,R~1=C_2H_5;2,R~1=n-C_4H_9;3,R~1=C_6H_5CH_2)     

铁双(双戊二烯巯基)环戊二烯基钛(Ⅳ), 锆(Ⅳ)的合成和结构表征

1, 1'-二巯基二茂铁分别和二氯二茂钛(Ⅳ), 二氯二茂锆(Ⅳ)在无水苯中在氨基钠存在下反应, 合成了两个未见报道的化合物Fe(η^5-C5H4S)2M(η^5-C5H5)Cl[M=Ti, Zr]。它们的组成和结构经元素分析,IR和^1H NMR得到证实。     

含二茂铁基的酰氧基二-(甲基环戊二烯基)钛衍生物的合成和性能研究

本文合成了十种新的含二茂铁基的酰氧基二-(甲基环戊二烯基)钛(η^5-CH~3C~5H~4)~2TC~2-nYn(Y=二茂铁羧酸基)。进行了元素分析, 讨论了它们的紫外和红外光谱, 及核磁共振谱。     

双（取代环戊二烯基）二氯化锆的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了双［１－苄基－１－乙基丙基环戊二烯基］二氯化锆［η５－Ｃ５Ｈ４Ｃ（Ｃ２Ｈ５）２ＣＨ２Ｃ６Ｈ５］２ＺｒＣｌ２（Ｉ）及（１，２－二异丁基－１，２－甲基－乙基桥联）双环戊二烯基二氯化锆［η５－Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ５Ｈ４－η５］ＺｒＣｌ２（Ⅱ）的结构。二者皆为单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，ａ＝１２．５８２（３），ｂ＝７．９９２（２），ｃ＝１４．９７９（３）Ａ，β＝１０１．６８（１）°，Ｖ＝１４７４．９（９）Ａ３，Ｍｒ＝６１２．８４，Ｚ＝２，Ｄｘ＝１．３８ｇ／ｃｍ３，μ＝５．６９ｃｍ（－１），Ｆ（０００）＝６４０，Ｒ＝０．０３３，Ｒω＝０．０３６。（Ⅱ）的空间群为Ｃｃ，ａ＝１３．３０９（３），ｂ＝９．５９１（１），ｃ＝１６．４４９（８）Ａ。β＝４．８３（３）°，Ｖ＝２０９．２（２）Ａ３，Ｍｒ＝４５８．６３，Ｚ＝４，Ｄｘ＝１．４５６ｇ／ｃｍ３，μ＝７．７７ｃｍ（－１），Ｆ（０００）＝９５２，Ｒ＝０．０５１，Ｒω＝０．０６１。化合物（Ｉ）以重叠式存在，两个苄基处于反式。晶体（Ⅱ）以交叉式存在，甲基、异丁基以反式构象存在。     

Gold and silver complexes with the ferrocenyl phosphine FcCH2PPh2

Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc = (eta5-C5H5)Fe(eta5-C5H4)] of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M = Au, Ag) have been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2CH2Fc)3]X (M = Au, X = ClO4; M = Ag, X = OTf) have been obtained from the corresponding gold and silver precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal structures of [AuR(PPh2CH2Fc)] (R = Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L = PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.     

The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes

The silyl ethers 3-But-2-(OSiMe3)C6H3CH=NR (2a-e) have been prepared by deprotonation of the known iminophenols (1a-e) and treatment with SiClMe3 (a, R = C6H5; b, R = 2,6-Pri2C6H3; c, R = 2,4,6-Me3C6H2; d, R = 2-C6H5C6H4; e, R = C6F5). 2a-c react with TiCl4 in hydrocarbon solvents to give the binuclear complexes [Ti{3-But-2-(O)C6H3CH=N(R)}Cl(mu-Cl3)TiCl3] (3a-c). The pentafluorophenyl species 2e reacts with TiCl4 to give the known complex Ti{3-But-2-(O)C6H3CH=N(R)}2Cl2. The mononuclear five-coordinate complex, Ti{3-But-2-(O)C6H3CH=N(2,4,6-Me3C6H2)}Cl3 (4c), was isolated after repeated recrystallisation of 3c. Performing the dehalosilylation reaction in the presence of tetrahydrofuran yields the octahedral, mononuclear complexes Ti{3-But-2-(O)C6H3CH=N(R)}Cl3(THF) (5a-e). The reaction with ZrCl4(THF)2 proceeds similarly to give complexes Zr{3-But-2-(O)C6H3CH=N(R)}Cl3(THF) (6b-e). The crystal structures of 3b, 4c, 5a, 5c, 5e, 6b, 6d, 6e and the salicylaldehyde titanium complex Ti{3-But-2-(O)C6H3CH=O}Cl3(THF) (7) have been determined. Activation of complexes 5a-e and 6b-e with MAO in an ethene saturated toluene solution gives polyethylene with at best high activity depending on the imine substituent.     

Synthesis and Characterization of Ferrocene Derived Cyclic Carbaphosphazenes

Dialkylamino substituted cyclic carbaphosphazenes, (R 2 NCN) 2 (NPCl 2 ) were prepared and reacted with the ferrocene derived hydroxymethyl phosphine sulfide FcCH(CH 3 )P(S)(CH 2 OH) 2 after dilithiation to yield a series of new spirocyclic derivatives of cyclic carbaphosphazenes having ferrocenyl pendant groups. To confirm the formation of six membered spirocycles and to compare their spectral features, transesterification reactions of FcCH(CH 3 )P(S)(CH 2 OH) 2 also were carried out with P(NR 2 ) 3 , yielding the six membered heterocycles FcCH 2 P(S)(CH 2 O) 2 PNR 2 (R = Me, Et). The compounds were characterized by 1 H, 31 P, 13 C NMR, mass spectra, and elemental analysis.     

Ansa-茂锆催化剂对乙烯/1-辛烯共聚合研究

乙烯与α 烯烃共聚合可制得线性低密度聚乙烯等重要塑料产品．用茂金属催化剂与甲基铝氧烷（ＭＡＯ）助催化剂合成的乙烯／α 烯烃共聚物具有共单体分布均匀，分子量分布窄等特点，其性能比传统的Ｚｉｅｇｌｅｒ Ｎａｔａ催化剂体系所得共聚物优越．茂金属化合物的结构...     

Lower homologues (methyl, ethyl) of diorganotin derivatives of germyl (substituted) propanoic acids: spectroscopic elucidations and biological studies

Some novel lower homologues of diorganotin derivatives of germyl substituted propanoic acids with general formula [Ar(3)GeCH(R(1))CH(R(2))COO](2)SnR(2)(3), where Ar = p-CH(3)C(6)H(4), C(6)H(5), R(1) = p-CH(3)C(6)H(4), p-CH(3)OC(6)H(4), o-CH(3)OC(6)H(4), C(6)H(5), R(2) = H, CH(3), R(3) = CH(3), C(2)H(5) have been prepared by the condensation reaction of dialkyltin oxide and triarylgermyl(substituted) propanoic acid in 1 : 2 M ratio, respectively, and were characterized by IR, multinuclear ((1)H, (13)C, (119)Sn) NMR, (119 m)Sn M?ssbauer spectroscopy. The synthesized compounds were also screened for their toxicity and possible antibacterial, antifungal activities and found some encouraging results.     

Electrospray ionization mass spectrometry of tribenzyltin substituted-phenoxyacetate compounds

Hydrolysis products of organotin compounds RC(6)H(4)OCH(2)COOSn(CH(2)ph)(3) (R = o-NO(2), 1; m-NO(2), 2; p-NO(2), 3; o-CH(3), 4; o-OCH(3), 5; o-Cl, 6; o-Br, 7) and RC(6)H(3)OCH(2)COOSn(CH(2)ph)(3) (R = o,o-2CH(3), 8, o-OCH(3), p-CHO, 9; o,p-2Cl, 10), produced in aqueous acetonitrile solution, have been investigated by electrospray mass spectrometry (MS) and MS(n) techniques. The complexes [Y(2)SnXR'](-), [Y(3)SnXR'](-), [Y(3)SnX(2)R'](-), [Y(2)SnX(3)R'](-), and fragment ions of [Y(3)SnR'](-), plus abundant RC(6)H(4)(or RC(6)H(3))OCH(2)COO(-) and RC(6)H(4)(or RC(6)H(3))O(-) ions are observed in negative mode, whereas the protonated molecular ion [M + H](+), complexes [Y(2)SnXR'](+), [Y(3)SnXR'](+), [Y(2)SnX(2)R'](+), [Y(3)SnX(2)R'](+), [Y(2)SnX(3)R'](+), [Y(3)SnX(3)R'](+), as well as [YSnXR'](+), [M - CH(2)ph](+), XSn(+), (phCH(2))(3)Sn(+), phCH(2)Sn(+) (Y = &bond;CH(2)ph, X = &bond;OOCCH(2)OC(6)H(4)R(or C(6)H(3)R)) are detected in the positive mode. Water adduct ions are seen in both modes. The assignments are facilitated by agreement between observed and calculated isotopic patterns and tandem mass spectrometry studies.     

Crystal Structure of catena-[(Tetrakis-μ2-acetato-μ2-4,4'-bipyridine) dicopper(Ⅱ)] Acetonitrile Solvate

The title compound,[Cu2(CH3COO)4(C8H10N2)]n·nCH3CN1 (C8H10N2,4,4'-bipy = 4,4'-bipyridine),has been solvothermally synthesized in CH3CN and characterized by X-ray diffraction.The crystal is of monoclinic,space group Cc with a = 22.626(6),b = 14.012(4),c =15.106(4) (A),β = 107.610(3)°,V = 4565(2) (A)3,C20H23Cu2N3O8,Mr = 560.49,Z = 8,Dc = 1.631 g/cm3,μ = 1.914 mm-1,Flack parameter = 0.48(1),F(000) = 2288,R = 0.042 and wR = 0.)98 for 8887 observed reflections (I ＞ 2σ(I)).It consists of nearly linear one-dimensional chains [Cu2(CH3COO)4(C8H10N2)]n derived from paddle-wheel [Cu2(CH3COO)4] unit linked by 4,4'-bipy,and CH3CN as guest molecule regularly decorates between the chains.     

Synthesis and Crystal Structure of Binuclear Copper （Ⅱ） Complex Containing （Dimethylaminomethyl）ferrocene

1 INTRODUCTION Transition metal complexes with ferrocene are of considerable interest in the past fifty years because of their novel structures and special properties[1, 2]. The chemistry of ferrocene and its derivatives has become richer and richer in the last decade. Many complexes containing ferrocenyl have been synthesized and characterized[3～5]. Recently we have reported the synthesis and crystal structure of dibromo[1,1?bis(diphenylphosphino)- ferrocene]cadmium (Ⅱ)[6]. Herein we…