• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Oxygen atom transfer in models for molybdenum enzymes: Isolation and structural, spectroscopic, and computational studies of intermediates in oxygen atom transfer from molybdenum(VI) to phosphorus(III)
【24h】

Oxygen atom transfer in models for molybdenum enzymes: Isolation and structural, spectroscopic, and computational studies of intermediates in oxygen atom transfer from molybdenum(VI) to phosphorus(III)

机译：钼酶模型中的氧原子转移：氧原子从钼（VI）转移到磷（III）的中间体的分离，结构，光谱和计算研究

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

Intermediates in the oxygen atom transfer from Mo-VI to P-III, [Tp(iPr)MoOX(OPR3)] (Tp(ipr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(ipr)-MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(iv) complexes possess local C, symmetry (by NMR spectroscopy) and exhibit IR bands assigned to v(Mo = O) (approximately 950 cm(-1)) and v(P = O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)-(OPMePh2)], and [Tp(iPr)MoOCl- (OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed Of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described.
机译：氧原子从Mo-VI转移至P-III的中间体，[Tp（iPr）MoOX（OPR3）]（Tp（ipr）=氢三（3-异丙基吡唑-1-基）硼酸盐; X = Cl-，酚盐，硫醇盐）已从[Tp（ipr）-MoO2X]与膦（PEt3，PMePh2，PPh3）的反应中分离出来。绿色的反磁性氧钼（iv）配合物具有局部C对称性（通过NMR光谱），并显示分配给v（Mo = O）（约950 cm（-1））和v（P = O）的IR波段（1140- 1083 cm（-1））振动。 [Tp（iPr）MoOX（OPEt3）]（X = OC6H4-2-sBu，SnBu），[Tp（iPr）MoO（OPh）-（OPMePh2）]和[Tp（iPr）的X射线晶体结构MoOCl-（OPPh3）]已确定。单体配合物表现出扭曲的八面体几何形状，配位球由三齿fac-Tp（iPr）和相互顺式单齿末端氧代，磷酰基（氧化膦）和单阴离子X配体组成。配合物的电子结构和稳定性已通过计算方法进行了探究，三维能级表面证实了低能位空间的存在，该空间限制了磷酰基配体的构象自由并抑制了氧原子的完全转移。还简要描述了配合物的反应性。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 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