Reactivity of the unsaturated complex [C6Me6)(2)Ru-2(mu(2)-H)(3)](+) toward phosphines: Synthesis and molecular structure of the dinuclear cations [C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) and characterization of the P-C bond activation intermediate

Tschan MJL; Cherioux F; Karmazin-Brelot L; Suss-Fink G

首页> 外文期刊>Organometallics >Reactivity of the unsaturated complex [C6Me6)(2)Ru-2(mu(2)-H)(3)](+) toward phosphines: Synthesis and molecular structure of the dinuclear cations [C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) and characterization of the P-C bond activation intermediate

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Reactivity of the unsaturated complex [C6Me6)(2)Ru-2(mu(2)-H)(3)](+) toward phosphines: Synthesis and molecular structure of the dinuclear cations [C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) and characterization of the P-C bond activation intermediate

机译：不饱和配合物[C6Me6）（2）Ru-2（mu（2）-H）（3）]（+）对膦的反应活性：双核阳离子[C6Me6]（2）Ru-2（ mu（2）-PR2）（mu（2）-H）（2）]（+）和PC键活化中间体的表征

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The unsaturated trihydrido complex [(C6Me6)(2)Ru-2(mu(2)-H)(3)](+) reacts with diaryl- or dialkyl-phosphines PR2H to give the dinuclear cations [(C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) (R= Ph, 1; R = t-Bu, 2). Surprisingly, complexes of the type [(C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) with R = Ph (1), n-Bu (3), n-Oct (4) are also accessible in high yield from the reaction of [(C6Me6)(2)Ru-2(mu(2)-H)(3)](+) with the corresponding triaryl- or trialkylphosphine PPh3, P(n-Bu)(3), or P(n-Oct)(3) by carbon-phosphorus bond cleavage. A possible intermediate of the reaction with PPh3, [(C6Me6)(2)Ru-2(mu(2)-PPh2)(mu(2)-H)(mu(2)-Ph)](+) (5), could be isolated from the reaction mixture as the tetrafluoroborate salt, the single-crystal X-ray structure analysis of which reveals a bridging phenyl ligand coordinated in an mu(1)-mu(2) fashion to the diruthenium backbone. With the mixed phosphine PMe2Ph, [(C6Me6)(2)Ru-2(mu(2)-H)(3)](+) reacts to give [(C6Me6)(2)Ru-2(mu(2)-PMe2)(mu(2)-H)(2)](+) (6) and the corresponding intermediate [(C6Me6)(2)Ru-2(mu(2)-PMe2)(mu(2)-H)(mu(2)-Ph)](+) (7). All dinuclear cations are isolated as the tetrafluoroborate salts.

机译：不饱和三氢配合物[（C6Me6）（2）Ru-2（mu（2）-H）（3）]（+）与二芳基或二烷基膦PR2H反应生成双核阳离子[（C6Me6）（2） Ru-2（mu（2）-PR2）（mu（2）-H）（2）]（+）（R = Ph，1; R = t-Bu，2）。令人惊讶的是，[[C6Me6）（2）Ru-2（mu（2）-PR2）（mu（2）-H）（2）]（+）类型的络合物，R = Ph（1），n-Bu （3），[[C6Me6）（2）Ru-2（mu（2）-H）（3）]（+）与相应的三芳基-的反应也可以高收率获得n-Oct（4）或三烷基膦PPh3，P（n-Bu）（3）或P（n-Oct）（3）通过碳-磷键裂解形成。与PPh3，[（C6Me6）（2）Ru-2（mu（2）-PPh2）（mu（2）-H）（mu（2）-Ph）]（+）的反应的可能中间体可以从反应混合物中以四氟硼酸盐的形式分离出来，其单晶X射线结构分析显示，以mu（1）-mu（2）方式与二价钌骨架配位的桥连苯基配体。 [[C6Me6）（2）Ru-2（mu（2）-H）（3）]（+）与混合膦PMe2Ph反应生成[（C6Me6）（2）Ru-2（mu（2）- PMe2）（mu（2）-H）（2）]（+）（6）和相应的中间体[（C6Me6）（2）Ru-2（mu（2）-PMe2）（mu（2）-H）（mu（2）-Ph）]（+）（7）。所有的双核阳离子均以四氟硼酸盐的形式被分离。

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《Organometallics》 |2005年第8期|共8页
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Tschan MJL; Cherioux F; Karmazin-Brelot L; Suss-Fink G;
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中图分类有机化学;
关键词
ARENE RUTHENIUM COMPLEXES; BRIDGED CARBONYL DIMERS; TRIRUTHENIUM CLUSTER COMPLEXES; TRANSFER HYDROGENATION; DECARBONYLATION REACTIONS; COORDINATED LIGANDS; OXIDATIVE ADDITIONS; HOMOGENEOUS HYDROGENATION; DIPHOSPHINE COMPLEXES; HYDRIDO COMPLEXES;

机译：芳烃钌络合物;桥碳酰二聚体;三HEN簇合物;转移加氢;脱碳反应;配位的液体;氧化助剂;均相加氢;二磷酸络合物;加氢;

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1. Reactivity of the unsaturated complex [C6Me6)(2)Ru-2(mu(2)-H)(3)](+) toward phosphines: Synthesis and molecular structure of the dinuclear cations [C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) and characterization of the P-C bond activation intermediate [J] . Tschan MJL, Cherioux F, Karmazin-Brelot L, Organometallics . 2005,第8期

机译：不饱和配合物[C6Me6）（2）Ru-2（mu（2）-H）（3）]（+）对膦的反应活性：双核阳离子[C6Me6]（2）Ru-2（ mu（2）-PR2）（mu（2）-H）（2）]（+）和PC键活化中间体的表征
2. Parallel coordination of hydrazine to diruthenium units: synthesis and molecular structure of the cationic complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(2)(mu(2)-eta(1),eta(1)-H2NNH2)](2+) and [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-H2NNH2)(m [J] . Jahncke M., Stoeckli-Evans H., Suss-Fink G., Journal of Organometallic Chemistry . 1998,第1a2期

机译：肼与钌单元的平行配位：阳离子配合物[（eta（6）-C6Me6）（2）Ru-2（mu（2）-H）（2）（mu（2）-eta（ 1），eta（1）-H2NNH2）]（2+）和[（eta（6）-C6Me6）（2）Ru-2（mu（2）-H）（mu（2）-eta（1）， eta（1）-H2NNH2）（米
3. PHOTOCHEMICALLY ACTIVATED PHOSPHORUS-CARBON BOND CLEAVAGE IN THE BINUCLEAR RUTHENIUM COMPLEX RU-2(CO)(6)(BPCD) - REDOX REACTIVITY, MOLECULAR ORBITAL PROPERTIES, AND X-RAY DIFFRACTION STRUCTURES OF RU-2(CO)(6)(BPCD) AND RU-2(CO)(6)[MU-C=C(PPH(2))C(O)C [J] . Shen HF., Richmond MG., Bott SG. Organometallics . 1995,第10期

机译：双核钌络合物RU-2（CO）（6）（BPCD）中的光化学活化的碳-碳键裂解-RU-2（CO）（6）（BPCD）的氧化还原反应性，分子轨道性质和X射线衍射结构）和RU-2（CO）（6）[MU-C = C（PPH（2））C（O）C
4. Application of reactive ion etching using C/sub 2/H/sub 6//H/sub 2/O/sub 2/ to fabricate a 1.48 /spl mu/m lnGaAsP/InP p-substrate buried-heterostructure laser diode [C] . Sugimoto, H., Isu, . 1992

机译：应用C / sub 2 / H / sub 6 // H / sub 2 / O / sub 2 /进行反应离子刻蚀，以制造1.48 / spl mu / m InGaAsP / InP p衬底埋入异质结构激光二极管
5. Mechanisms of electron transfer and hydrogen activation in selected triruthenium clusters with multiple bridging ligands. Part I. The attenuation of radical reactivity in triruthenium trihydrido(alkylidyne) clusters. Electrochemistry and kinetics of decomposition of the 47-electron cluster radical, via a disproportionation path. Part II. The activation of molecular hydrogen at transition metal centers via kinetics and mechanism of reversible oxidative addition of hydrogen across the metal-metal bond of (mu-hydrogen)(2)Ruthenium(3)(Carbon monoxide)(8)(mu-phosphorus(t-BU)(2))(2). [D] . Bierdeman, David John. 2000

机译：具有多个桥联配体的选定三钌簇中电子转移和氢活化的机理。第一部分。三氢三钌（亚烷基）簇中自由基反应性的减弱。通过歧化路径分解47电子簇自由基的电化学和动力学。第二部分通过（mu-hydrogen）（2）钌（3）（一氧化碳）（8）（mu-phosphorus（）的金属-金属键上氢的可逆氧化加成反应的动力学和机理激活过渡金属中心的分子氢t-BU）（2））（2）。
6. ClpX protein of Escherichia coli activates bacteriophage Mu transposase in the strand transfer complex for initiation of Mu DNA synthesis. [O] . R Kruklitis, D J Welty, H Nakai 1996

机译：大肠杆菌的ClpX蛋白激活链转移复合物中的噬菌体Mu转座酶以启动Mu DNA合成。
7. Highly Selective Hydrogenation of Carbon–Carbon Multiple Bonds Catalyzed by the Cation [(C6Me6)2Ru2(PPh2)H2]+: Molecular Structure of [(C6Me6)2Ru2(PPh2)(CHCHPh)H]+, a Possible Intermediate in the Case of Phenylacetylene Hydrogenation [O] . J.-L. Tschan, Mathieu, Süss-Fink, Georg, Cherioux, Frederic, 2007

机译：阳离子[（C6Me6）2Ru2（PPh2）H2] +催化的碳-碳多键的高选择性加氢：[（C6Me6）2Ru2（PPh2）（CHCHPh）H] +的分子结构，在以下情况下可能是中间产物苯乙炔加氢
8. Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 90. (1) Synthesis of the Complexes (W2M2(mu-CO)(mu-CMe)(mu3-CMe)-(Mu-PPh2)2(CO)3(eta-C5H5)2) (M = Rh or Ir) and Related Tetra- and Penta-nuclear Metal Compounds: Interconversion of Ketenyl and Lambda(5) -Phospha-alkyne Ligands Bridging Tungsten-Rhodium Bonds. [R] . Davies, S. J., Stone, F. G. 1989

机译：具有桥接卡宾或卡宾配体的多核金属配合物的化学。部分90.（1）配合物的合成（W2m2（mu-CO）（mu-Cme）（mu3-Cme） - （mu-pph2）2（CO）3（eta-C5H5）2）（m = Rh或Ir）和相关的四核和五核金属化合物：Ketenyl和Lambda（5）-phospha-alkyne配体桥联钨 - 铑键的相互转化。

Reactivity of the unsaturated complex [C6Me6)(2)Ru-2(mu(2)-H)(3)](+) toward phosphines: Synthesis and molecular structure of the dinuclear cations [C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) and characterization of the P-C bond activation intermediate

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