• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Transition metal complexes with sulfur ligands. 130. Synthesis, structure, and reactivity of the sulfur-rich ruthenium hydride complexes [Ru(H)(PR3)('S-4')(-) and the eta(2)-H-2 complex [Ru(H-2)(PCy3)('S-4')] (R = Ph, Pr-i, Cy; 'S-4'(2-) = 1,2-bis((2
【24h】

Transition metal complexes with sulfur ligands. 130. Synthesis, structure, and reactivity of the sulfur-rich ruthenium hydride complexes [Ru(H)(PR3)('S-4')(-) and the eta(2)-H-2 complex [Ru(H-2)(PCy3)('S-4')] (R = Ph, Pr-i, Cy; 'S-4'(2-) = 1,2-bis((2

机译：具有硫配体的过渡金属配合物。 130.富硫氢化钌络合物[Ru（H）（PR3）（'S-4'）（-）和eta（2）-H-2络合物[Ru（H- 2）（PCy3）（'S-4'）]（R = Ph，Pr-i，Cy;'S-4'（2-）= 1,2-bis（（2

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Hydride and eta(2)-H-2 ruthenium complexes with sulfur-rich coordination spheres were synthesized. Substitution of either DMSO or PPh3 in [Ru(DMSO)(PR3)('S-4')] and [Ru(PPh3)(2)('S-4')] by hydride anions from LiAlH4 or NaBEt3H yielded [Ru(H)(PR3)('S4('))](-) complexes (R = Pr-i, Ph, Cy; 'S-4'(2-) = 1,2-bis((2-mercaptophenyl)thio)ethane(2-)). They were isolated as [Li(THF)(Et2O)][Ru(H)(PR3)('S-4')] (R = Pr-i (1a), Cy (1b), Na[Ru(H)(PCy3)('S-4')]. 2BEt(3). 0.5DMSO (2a), and the solvent-free Na[Ru(H)(PPh3)('S-4')]. 2BEt(3) (2b). X-ray structure determinations of 1a . 0.5Et(2)O and 1b . Et2O showed that in both complexes pseudaoctahedral [Ru(H)(PR3)('S-4')]- anions an bridged to pseudotetrahedral [Li(THF)(Et2O)] cations via the hydride Ligand and one thiolate donor of the 'S-4'(2-) ligand (crystal data: 1a, monoclinic, P2(1), a = 1401.6(2) pm, b = 1045.2(3) pm, c = 2590.6(4) pm, beta = 95.04(1)degrees, V = 3.780(1) nm(3), Z = 4; 1b, triclinic, P (1) over bar, a = 1264.2(1) pm, b = 1322.9(3) pm, c = 1569.5(2) pm, alpha = 88.96(1)degrees, beta = 83.48(1)degrees, gamma = 62.16(1)degrees, V = 2.3042(6) nm(3), Z = 2). Short intramolecular C-H ... H-Ru contacts (approximate to 230 pm) between the hydride ligands, phosphine substituents, and lithium-coordinated Et2O molecules indicate "unconventional" hydrogen bonds. They potentially help to decrease the hydridic character of the hydride ligand to such an extent that no structural hydride trans influence can be observed in the solid stare. In solution at room temperature, all hydride complexes 1a-2b rapidly release H-2 or HD, when treated with CH3OH or CD3OD. Low-temperature H-1 and H-2 NMR spectroscopy between -20 and -80 degrees C showed that initially eta(2)-H-2 or eta(2)-HD complexes form. Their formation explains the observed scrambling between protons and hydride ligands, which requires a heterolytic cleavage of dihydrogen. A 1:1:1 tripler at delta = -6.5 ppm ((1)J(HD) = 32 Hz, (2)J(PH) = 5 Hz) and a relaxation time of T-1(min) = 4 ms (-60 degrees C, 270 MHz) firmly established the formation of the eta(2)-dihydrogen complexes. The reversibility of H-2 release and uptake by [Ru(PCy3)('S4')1 fragments and the heterolytic cleavage of H-2 in [Ru(eta(2)-H-2)(PCy3)('S-4')] was further ascertained by the reaction of [Ru(DMSO)(PCy3)('S-4')] with Ha in the presence of NaOMe, yielding the [Ru(H)(PCy3)('S-4')](-) anion. The relevance of the complexes and their reactions for the heterolytic H-2 activation at the transition metal sulfur sites of hydrogenases is discussed. [References: 103]
机译：合成了具有富硫配位球的氢化物和eta（2）-H-2钌配合物。用LiAlH4或NaBEt3H的氢化物阴离子取代[Ru（DMSO）（PR3）（'S-4'）]和[Ru（PPh3）（2）（'S-4'）]中的DMSO或PPh3产生[Ru （H）（PR3）（'S4（'））]（-）配合物（R = Pr-i，Ph，Cy;'S-4'（2-）= 1,2-bis（（2-巯基苯基）硫）乙烷（2-））。它们被分离为[Li（THF）（Et2O）] [Ru（H）（PR3）（'S-4'）]（R = Pr-i（1a），Cy（1b），Na [Ru（H） （PCy3）（'S-4'）]。2BEt（3）。0.5DMSO（2a）和无溶剂的Na [Ru（H）（PPh3）（'S-4'）]。2BEt（3） （2b）。1a。0.5Et（2）O和1b.Et2O的X射线结构测定表明，在两种络合物中，假八面体[Ru（H）（PR3）（'S-4'）]-阴离子桥连至拟四面体[Li（THF）（Et2O）]阳离子通过氢化物配体和'S-4'（2-）配体的一个硫醇盐供体（晶体数据：1a，单斜晶系，P2（1）/ n，a = 1401.6（2） ）pm，b = 1045.2（3）pm，c = 2590.6（4）pm，beta = 95.04（1）度，V = 3.780（1）nm（3），Z = 4; 1b，三斜晶系，P（1）超过bar，a = 1264.2（1）pm，b = 1322.9（3）pm，c = 1569.5（2）pm，alpha = 88.96（1）度，beta = 83.48（1）度，gamma = 62.16（1）度，V = 2.3042（6）nm（3），Z = 2）。氢化物配体，膦取代基和锂配位的Et2O分子之间的短分子CH ... H-Ru接触（约230 pm）表明“非常规氢键。它们潜在这有助于将氢化物配体的氢化特性降低到一定程度，以致在固体凝视中没有观察到结构氢化物的反式影响。在室温下的溶液中，当用CH3OH或CD3OD处理时，所有氢化物配合物1a-2b迅速释放H-2或HD。 -20至-80摄氏度之间的低温H-1和H-2 NMR光谱表明，最初形成eta（2）-H-2或eta（2）-HD络合物。它们的形成解释了所观察到的质子与氢化物配体之间的争夺，这需要二氢的杂化裂解。 1：delta三倍频器，增量为-6.5 ppm（（1）J（HD）= 32 Hz，（2）J（PH）= 5 Hz），松弛时间为T-1（min）= 4 ms （-60摄氏度，270 MHz）牢固地建立了eta（2）-二氢配合物的形成。 H-2释放和被[Ru（PCy3）（'S4'）1片段摄取的可逆性和H-2在[Ru（eta（2）-H-2）（PCy3）（'S-在NaOMe存在下，通过[Ru（DMSO）（PCy3）（'S-4'）]与Ha的反应进一步确定[4'）]，得到[Ru（H）（PCy3）（'S-4 '）]（-）阴离子。讨论了配合物的相关性及其在氢化酶过渡金属硫位上杂化H-2活化的反应。 [参考：103]

著录项

相似文献

  • 外文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号