1,1'-(四甲基二硅撑)双[环戊二烯基三羰基钼配合物]的合成及结构

1,2-二环戊二烯基四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双[环戊二烯基负离子盐],后者随即与六羰基钼反应即形成1,1'-(四 甲基二硅撑)双[环戊二烯基三羰基钼负离子盐],分别与四种不同的卤化物反应,生成在钼原子上发生烃基化的产物与冰醋酸作用,随即分别与CCl~4及NBS反应,生成相应的钼氯化物和钼溴化物作用发生氧化偶联反应,生成Mo-Mo键断裂的钼碘化物,以元素分析、IR及^1HNMR表征了2-9的结构.并对5的单晶进行了X射线衍射分析.它的晶体属三斜晶系,PI空间群,晶体学数据:偏差因子R=0.043,R~W=0.055.     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六羰基钼的反应

１,２－双（四甲基环戊二在）四甲基二硅烷与正丁基锂作用生成（四甲基二硅撑）双（四甲基环戊二烯基负离子盐）,后者随即与六羰基钼反应形成１,１＇－（四甲基二硅撑）双（四甲基环戊二烯基钼负离子盐）－－（Ｍｅ２ＳｉＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３－Ｌｉ＾＋〗２（１）,１与冰醋酸作用,随即分别与ＣＣＩ４,ＮＢＳ及Ｉ２反应,生成相应的钼卤化合物（Ｍｅ２ＳＩＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３Ｘ〗２〖Ｘ     

1,1′-(四甲基二硅撑)双[环戊二烯基三羰基钼配合物]的合成及结构

1,2-二环戊二烯基四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双[环戊二烯基负离子盐],后者随即与六羰基钼反应即形成1,1′-(四甲基二硅撑)双[环戊二烯基三羰基钼负离子盐],(Me_2SiSiMe_2)[Cp′(CO)_3~-Li~+]_2(1)、1分别与四种不同的卤化物反应,生成在钼原子上发生烃基化的产物(Me_2SiSiMe_2)[Cp′Mo(CO)_3R]_2(R:CH_3,2;C_2H_5,3;=PhCH_2,4;CH_2COOC_2H_5,5).1与林醋酸作用,随即分别与CCl4及NBS反应,生成相应的钼氯化物和钼溴化物(Me_2SiSiMe_2)[Cp′MO(CO)_3X]_2(X:Gl,6;Br,7).1与Fe_2(SO_4)_3/H_3O~+作用发生氧化偶联反应,生成Mo—Mo键双核产物(Me_2SiSiMe_2)[Cp′Mo(CO)_3]_2(8).8在氯仿中与碘反应,又生成Mo—Mo键断裂的钼碘化物(Me_2SiSiMe_2)[Cp′Mo(CO)_3I]_2(9).以元素分析、IR及~1H NMR表征了2—9的结构.并对5的单晶进行了X射线衍射分析.它的晶体属三斜晶系,Pl空间群,晶体学数据:a=1.1447(2),b=1.36(?)0(4),c=1.4125(2)nm;β=60.01(1)~°.V=1.6336nm~3,Z=2,D_o=1.583g·cm~(-2).μ=8.7cm~(-1),F(000)=788.偏差因子R=0.043,R_w=0.055.     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六碳基钼的反应

1,2-双(四甲基环戊二烯基)四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双(四甲基环戊二烯基负离子盐),后者随即与六碳基钼反应形成1,1'-(四甲基二硅撑)双(四甲基环戊二烯基铝负离子盐)-(Me₂SiSiMe₂)[Me₄CpMo(CO)₃-Li⁺]₂(I),I与冰醋酸作用,随即分别与CCl₄,NBS及I₂反应,生成相应的铝卤化合物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃X]₂[X=Cl(1),Br(2),I(3)].I与CH₃I反应,在钼原子上发生烃基化,得到产物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃Me]₂(4);I与单质I₂直接反应,生成脱硅桥产物Me₄Cp(CO)>₃I(5).经元素分析、IR及¹HNMR表征了化合物1-5的结构。     

1,1'-(四甲基二硅氧撑)双[环戊二烯基羰基钼配合物]的合成及结构

以1,3-二环戊烯基四甲基二硅氧烷相继与n-BuLi及Mo(CO)~6反应生成1,1'-(四甲基二硅氧撑)双[环戊二烯基羰基钼负离子盐](I),I分别与多种卤化物反应生成在钼原子上引入其它基团的衍生物,(Me~2SiOSiMe~2)[C~5H~4Mo(CO)~3R]~2.以元素分析、IR及^1HNMR谱表征了这些化合物的结构,并对其中之一的单晶(R=1)进行了X射线衍射分析.晶体属单斜晶系,P2~1/n空间群,晶体学数据,a=0.8707(2),b=1.0746(4),c=2.9719(8)nm,β=91.18(2)°,Ⅴ=2.7799nm^3,z=4,D~c=2.09g.cm^-3.最终偏差因子R为0.067.     

1,1'-(四甲基二硅氧撑)双[环戊二烯基羰基钼配合物]的合成及结构

以1,3-二环戊烯基四甲基二硅氧烷相继与n-BuLi及Mo(CO)~6反应生成1,1'-(四甲基二硅氧撑)双[环戊二烯基羰基钼负离子盐](I),I分别与多种卤化物反应生成在钼原子上引入其它基团的衍生物,(Me~2SiOSiMe~2)[C~5H~4Mo(CO)~3R]~2.以元素分析、IR及^1HNMR谱表征了这些化合物的结构,并对其中之一的单晶(R=1)进行了X射线衍射分析.晶体属单斜晶系,P2~1/n空间群,晶体学数据,a=0.8707(2),b=1.0746(4),c=2.9719(8)nm,β=91.18(2)°,Ⅴ=2.7799nm^3,z=4,D~c=2.09g.cm^-3.最终偏差因子R为0.067.     

1,1′-(四甲基二硅氧撑)双[环戊二烯基羰基钼配合物]的合成及结构

以1,3-二环戊二烯基四甲基二硅氧烷相继与n-BuLi及Mo(CO)_6反应生成1,1'-(四甲基二硅氧撑)双[环戊二烯基三羰基钼负离子盐](Ⅰ),Ⅰ分别与多种卤化物反应生成在钼原子上引入其它基团的衍生物,(Me_2SiOSiMe_2)[C_5H_4Mo(CO)_3R]_2.以元素分析、IR及~1HNMR谱表征了这些化合物的结构,并对其中之一的单晶(R=I>进行了X射线衍射分析.晶体属单斜晶系,P21/n空间群.晶体学数据.a=0.8707(2),b=1.0746(4),c=2.9719(8)nm;β=91.18(2)°,V=2.7799nm~3,Z=4,D_c=2.09g·cm~(-3)最终偏差因子R为0.067.     

三羰基全甲基硅基环戊二烯基钼衍生物的合成与表征

通过三羰基（五甲基二硅基）环戊二烯基钼负离子盐与卤代烃（ＥｔＩ，ＰｈＣＨ２Ｃｌ，ＣｌＣＨ２ＣＯＯＥｔ，Ｉ（ＣＨ２）４Ｉ）进行基化反应合成其烷基钼化合物。用六甲基三硅二氧烷桥联双（三羰基环戊二烯基钼）负离子经冰醋酸处理，硫酸铁氧化偶联成钼－钼键双核化合物，经碘裂解后钼－钼键生成六甲基三硅二氧烷桥联双（三羰基环戊二烯基碘钼）化合物。以元素分析，ＩＲ和１ＨＮＭＲ谱表征了化合物的结构。     

四羰基二(五甲二硅基环戊二烯基)二钼的合成及反应

本文进一步报道四羰基二(五甲二硅基环戊二烯基)二铜的合成及反应, 五甲二硅基环戊二烯与六羰基钼在甲苯中加热回流9h, 即生成含Mo-Mo键的双核钼配合物1, 1在甲苯中进一步加热回流, 则发生脱羰而生成标题化合物。     

四甲基硅锗桥连双环戊二烯基及双(四甲基环戊二烯基)四羰 基二铁的合成、结 构及热重排反应

1,2-二氯四甲基硅锗烷分别与环戊二烯基锂及四甲基环戊二烯基锂反应得到两个新的双齿配体：C5H5Me2SiGeMe2C5H5(9)和C5HMe4Me2SiGeMe2C5HMe4(10).配体9和10分别与Fe(CO)5在二甲苯中加热生成四甲基硅锗桥连双环戊二烯基四羰基二铁(11)和四甲基硅锗桥连双(四甲基环戊二烯基)四羰基二铁(13).11和13均可发生热重排反应,生成[(η^5-C5R4)Fe(CO)2]2(μ-Me2Si)(μ-Me2Ge)(R=H,12;R=Me,14)。测定了化合物11,12,13及14的晶体结构,讨论了桥连四甲基环戊二烯基配体的位阻效应对其某些结构参数以及重排反应性的影响。     

三(三甲硅基)环戊二烯基三羰基钼负离子的反应性

三(三甲硅基)环戊二烯基三羰基钼负离子锂盐[{η^5-(Me~3Si)~3C~5H~2}Mo(CO)~3]^-Li^+(1), 分别与MeI、phCH~2Cl及ClCH~2COOC~2H~5反应生成相应的烃基化钼衍生物[{η^5-(Me~3Si)~3C~5H~2}Mo(CO)~3R,] (R=-CH~3, 2; -CH~2ph, 3;-CH~2COOC~2H~5, 4)。1与PCl~3反应除得到预期的钼氯化物[{η^5-(Me~3Si)~3C~5H~2}Mo(CO)~3Cl](5)外, 主要得到钼磷氯化物[{η^5-(Me~3Si)~3C~5H~2}Mo(CO)~3PCl~2] 6; 1与碘反应得到钼碘化物[{η^5-(Me~3Si)~3C~5H~2}Mo(CO)~3I] 7; 1与HOAc作用后分别和CCl~4、NBS室温反应, 仅分离到脱去一个Me~3Si的钼卤化物[{η^5-(Me~3Si)~2C~5H~2}Mo(CO)~3X], (X:Cl, 8; Br, 9)。     

New disulfido molybdenum-manganese complexes exhibit facile addition of small molecules to the sulfur atoms

The reaction of Mn(2)(CO)(7)(mu-S2) (1) with [CpMo(CO)(3)](2) (Cp = C(5)H(5)) and [Cp*Mo(CO)(3)](2) (Cp* = C(5)(CH(3))(5)) yielded the new mixed-metal disulfide complexes CpMoMn(CO)(5)(mu-S2) (2) and Cp*MoMn(CO)(5)(mu-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) A and S-S = 2.042(2) and 1.9973(10) A for 2 and 3, respectively. A tetranuclear metal side product CpMoMn(3)(CO)(13)(mu3-S)(mu4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)(3)](2). Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn(CO)(5)[mu-SC(=O)S] (5) and Cp*MoMn(CO)(5)[mu-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)(5)[mu-S(C=NBu(t))S] (7) and Cp*MoMn(CO)(5)[mu-S(C=NBu(t))S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn(CO)(5)(mu-SCH(2)CH(2)S) (9), Cp*MoMn(CO)(5)(mu-SCH(2)CH(2)S) (10), CpMoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (11), and Cp*MoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)(5)[mu-SCH(2)C(=CH(2))S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.     

(四甲基二硅撑)二(3-三甲硅基环戊二烯基)四羰基二铁及其相关化合物的合成及结构

1,2-二(三甲硅基环戊二烯基)四甲基二硅烷与Fe(CO)5在二甲苯中于105～110℃反应除分离到少量标题化合物(Me2SiSiMe2)[η-(3-Me3SiC5H3Fe(CO)]2(μ-CO)2(5)外,主要是生成了脱Me3Si基的产物(Me2SiSiMe2)[η-C5H4Fe(CO)]2(μ-CO)2(1)及1的热重排异构体[Me2SiC5H4-Fe(CO)2]2(2).将5的二甲苯溶液加热回流18h,则转化为其异构体[Me2Si(Me3SiC5H3)Fe(CO)2]2(6).脱硅基发生在由相应反应物制备5的过程中。且脱硅基是与反应物中(Me2SiSiMe2)桥的存在有关。5的晶体结构经X射线衍射测定属单斜晶系,P21/m空间群,晶体学数据:a=0.6780(1)nm,b=2.2303(9)nm,c=0.9988(1)nn,;β=98.96(1)°,V=1.4960nm3.Z=2,Dc=1.36g/cm3.     

Reduction of (imine)Pt(IV) to (imine)Pt(II) complexes with carbonyl-stabilized phosphorus ylides

A novel method is reported for generation of the difficult-to-obtain (imine)Pt(II) compounds that involves reduction of the corresponding readily available Pt(IV)-based imines by carbonyl-stabilized phosphorus ylides, Ph3P=CHCO2R, in nonaqueous media. The reaction between neutral (imino)Pt(IV) compounds [PtCl4[NH=C(Me)ON=CR1R2]2] [R1R2 = Me2, (CH2)4, (CH2)5, (Me)C(Me)=NOH], [PtCl4[NH=C(Me)ONR2]2] (R = Me, Et, CH2Ph), (R1 = H; R2 = Ph or C6H4Me; R3 = Me) as well as anionic-type platinum(IV) complexes (Ph3PCH2Ph)[PtCl5[NH=C(Me)ON=CR2]] [R2 = Me2, (CH2)4, (CH2)5] and 1 equiv of Ph3P=CHCO2R (R = Me, Et) proceeds under mild conditions (ca. 4 h, room temperature) to give selectively the platinum(II) products (in good to excellent isolated yields) without further reduction of the platinum center. All thus prepared compounds (excluding previously described Delta4-1,2,4-oxadiazoline complexes) were characterized by elemental analyses, FAB mass spectrometry, IR and 1H, 13C[1H], 31P[1H] and 195Pt NMR spectroscopies, and X-ray single-crystal diffractometry, the latter for [PtCl2[NH=C(Me)ON=CMe2]2] [crystal system tetragonal, space group P4(2)/n (No. 86), a = b = 10.5050(10) A, c = 15.916(3) A] and (Ph3PCH2CO2Me)[PtCl3(NCMe)] [crystal system orthorhombic, space group Pna2(1) (No. 33), a = 19.661(7) A, b = 12.486(4) A, c = 10.149(3) A]. The reaction is also extended to a variety of other Pt(II)/Pt(IV) couples, and the ylides Ph3P=CHCO2R are introduced as mild and selective reducing agents of wide applicability for the conversion of Pt(IV) to Pt(II) species in nonaqueous media, a route that is especially useful in the case of compounds that cannot be prepared directly from Pt(II) precursors, and for the generation of systematic series of Pt(II)/Pt(IV) complexes for biological studies.     

Organoiron compounds derived from the indium 'carbene analogues', [In(N(Ar)C(Me))2CH] (Ar = dipp = 2,6-iPr2C6H3; = Mes = 2,4,6-Me3C6H2)

Oxidative insertion of the In(I) 'carbene analogues', [In{N(Dipp)C(Me))2CH] (Ar = Dipp = 2,6-iPr2C6H3; Ar = Mes = 2,4,6-Me3C6H2) into the Fe-I bond of [CpFe(CO)2I] occurred cleanly and under mild conditions to yield the In(III) compounds [CH((CH3)2CN-2,6-iPr2C6H3)2In(I)FeCp(CO)2] and [CH( (CH3)2CN-2,4,6-Me3C6H3)2In(I)FeCp(CO)2], which have been fully characterised in solution and the solid state. Attempts to abstract the iodide anion from [CH( (CH3)2CN-2,6-iPr2C6H3)2In(I)FeCp(CO)2] to form cationic species containing a coordinated indium diyl were unsuccessful and resulted in a complex mixture of products from which two ionic species were isolated. Neither cation was found to contain indium by X-ray crystallographic analysis. These observations were indicative of ill-defined decomposition pathways as have been noted by previous workers. A further attempt to form a cationic iron species containing a coordinated [In(N(Dipp)C(Me) )2CH] fragment resulted in oxidation of the iron centre from Fe(II) to Fe(III), with deposition of indium metal, and the isolation of a cationic Fe(III) beta-diketiminate complex.     

昆虫信息素的结构鉴定和合成XXIV: (TR,8S)-(+)-和(7S,8R)-(-)-午毒蛾性信息素的合成及β-羟基硅烷的立体化学

从Sharpless不对称环氧化反应所得的光学活性环氧醛(e.e.96-97%)与三甲基硅锂试剂反应,得到β-羟基硅烷.它们经转化成乙酰氧基化合物后,再通过β-乙酰氧基硅烷的消除反应和均相催化氢化即得到两个标题化合物.对β-羟基硅烷的各非对映异构体的构型进行了测定.     

手性炔基亚砜作为二碳合成子在生物卤介不对称合成中的应用

本文报导了手性炔基亚砜的制备及其在四氢异喹啉及四氢咔啉生物碱对映体选择性合成中的应用。     

S树兰烯( 烯)类似物的合成

本文报导了树兰烯(即钴钯烯)的几个类似物(6a-d和7a-d)的合成, 并讨论了有关这些化合物的形成反应的构象效应。