首页> 外文学位 >I. Synthesis, reactivity, and structural studies of rhodium(III) and rhodium(II) complexes of novel bis(oxazoline) pincer ligands. II. Synthesis and reactivity of novel rhenium methylidene complexes.

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I. Synthesis, reactivity, and structural studies of rhodium(III) and rhodium(II) complexes of novel bis(oxazoline) pincer ligands. II. Synthesis and reactivity of novel rhenium methylidene complexes.

机译：I.新型双（恶唑啉）夹钳配体的铑（III）和铑（II）配合物的合成，反应性和结构研究。二。新型methyl亚甲基配合物的合成和反应性。

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Chapter 1. A series of novel C2-symmetric bisoxazoline ligands (benbox and benboxMe₂) have been prepared. A variety of coordinatively unsaturated rhodium(III) complexes (3a–g, 4a–g ) have been isolated. Trapping reactions of the agostically-stabilized complex [RhCl₂{lcub}(S,S)-ib-benbox(Me₂){rcub}] (4d) are described. Metal-to-aryl methyl migration reactions are described for the complex [RhMe{lcub}(S,S)-ip-benbox(Me₂){rcub}][BArf] (11c). Full characterization details and reactivity studies of air-stable, isolable, mononuclear, paramagnetic rhodium(II) complexes [RhCl₂{lcub}(S,S)-tb-benbox(Me₂){rcub}(H)] (15e) and [RhCl₂{lcub}dm-benbox(Me₂)H{rcub}] (15g) are reported.; Chapter 2. The synthesis and structural properties of three new hydridorhodium(III) complexes are reported. Hydrogenolysis of the cyclometallated rhodium dichloride complexes [RhCl₂{lcub}(S,S )-benbox(Me₂){rcub}] (1a–c) leads to formation of the new complexes [RhCl₂(H){lcub}(S,S)-ip-benbox(Me₂)H{rcub}] (2a–c) in 45% to 85% yield. Compounds 2a–c were found to have unusual features by NMR spectroscopy: in particular, downfield shifted aryl proton resonances (8.88–9.03 ppm) that coupled to the rhodium hydride resonances. Using X-Ray crystallographic studies and a variety of solid and solution state characterization techniques, these features were attributed to the presence of preagostic bonding in 2a–c. Preagostic bonding is a rare phenomenon that shares attributes with both agostic and hydrogen bonding interactions.; Chapter 3. A family of bis(oxazoline) complexes of coordinatively unsaturated monomeric rhodium(II) (2a,b, 3a,b) are described. These complexes serve as catalysts for cyclopropanation of olefins by ethyl diazoacetate, giving excellent yields (66–94%). Enantioselectivities for the cis product isomers are high (61–84%). The reaction shows an unusual preference for formation of the cis isomers. Catalytic asymmetric aziridination of N-aryl imines with ethyl diazoacetate is also described.; Chapter 4. The synthesis and reactivity of two novel rhenium methylidene complexes is described. Protonolysis of the new dimethylrhenium(III) compound Cp*(PMe₃)₂Re(CH₃)₂ ( 3) leads to formation of the surprising hydridorhenium methylidene compound [Cp*(PMe₃)₂Re(CH₂)(H)][OTf] ( 5), which was characterized spectroscopically at low temperature. (Abstract shortened by UMI.)

机译：第1章。制备了一系列新颖的C2对称双恶唑啉配体（benbox和benboxMe _{2 ）。已分离出各种配位不饱和铑（III）配合物（ 3a–g，4a–g ）。先前稳定的复合物[RhCl _{2 {lcub}（S，S）-ib-benbox（Me _{2 ）{rcub}]的诱捕反应（ 4d ）进行了说明。描述了配合物[RhMe {lcub}（S，S）-ip-benbox（Me _{2 ）{rcub}] [BArf]（ 11c ）。空气稳定，可分离的单核顺磁性铑（II）配合物[RhCl _{2 {lcub}（S，S）-tb-benbox（Me _{2 < / sub>）{rcub}（H）]（ 15e ）和[RhCl _{2 {lcub} dm-benbox（Me _{2 ）H {rcub}]（ 15g ）。第2章。报道了三种新型氢化铑（III）配合物的合成和结构性质。环金属化二氯化铑配合物[RhCl _{2 {lcub}（）-benbox（Me _{2 ）{rcub}的氢解作用]（ 1a–c ）导致形成新的复合物[RhCl _{2 （H）{lcub}（ S，S ）-ip-benbox （Me _{2 ）H {rcub}]（ 2a–c ），产率为45％至85％。 NMR光谱发现化合物 2a–c 具有不寻常的特征：特别是下场位移的芳基质子共振（8.88–9.03 ppm）与氢化铑共振耦合。使用X射线晶体学研究以及各种固态和溶液状态表征技术，这些特征归因于 2a–c 中的前声波键合。前声波键合是一种罕见的现象，与原子键合和氢键键合具有共同的属性。第3章。描述了配位不饱和单体铑（II）（ 2a，b，3a，b ）的双（恶唑啉）配合物家族。这些配合物可作为重氮乙酸乙酯对烯烃进行环丙烷化的催化剂，具有出色的收率（66-94％）。 cis 产品异构体的对映选择性很高（61–84％）。该反应显示出对形成顺式异构体的异常偏好。还描述了 N -芳基亚胺与重氮乙酸乙酯的催化不对称叠氮化。第4章。描述了两种新型rh亚甲基配合物的合成和反应性。新型二甲基hen（III）化合物Cp *（PMe _{3 ）_{2 Re（CH _{3 ）_{2 的质子分解（ 3 ）导致令人惊讶的亚甲基氢化hen鎓化合物[Cp *（PMe _{3 ）_{2 Re（CH _{2 ）（H）] [OTf]（ 5 ），其在低温下具有光谱特征。（摘要由UMI缩短。）}}}}}}}}}}}}}}}}}}}

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作者
Krumper, Jennifer.;
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作者单位

University of California, Berkeley.;

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授予单位 University of California, Berkeley.;
学科 Chemistry Inorganic.; Chemistry Organic.
学位 Ph.D.
年度 2003
页码 211 p.
总页数 211
原文格式 PDF
正文语种 eng
中图分类无机化学;有机化学;
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I. Synthesis, reactivity, and structural studies of rhodium(III) and rhodium(II) complexes of novel bis(oxazoline) pincer ligands. II. Synthesis and reactivity of novel rhenium methylidene complexes.

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