SYNTHESIS AND REDOX REACTION PROPERTIES OF OXOMOLYBDENUM COMPLEXES WITH 1,1-DITHIOLATO LIGANDS

1,1-二硫醇配体氧代钼配合物的合成及其氧化还原反应性质

• 批准号: 07640734
• 负责人: UNOURA Kei
• 金额: $ 1.47万
• 依托单位: Yamagata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640734/
• 关键词: OXOMOLYBDENUM COMPLEXES; 1,1-DITHIOLATES; ELECTROCHEMISTRY; OXYGEN ATOM TRANSFER; KINETICS; OXOVANADIUM COMPLEXES

We have invetigated the redox properties of oxomolybdenum complexes with 1,1-dithiolates. The results of this study were sumarized as follows.1) The electrochemical properties of a series of cis-dioxobis (dithiocarbamato) molybdenum (VI) complexes [MoO_2 (RR'dtc) _2] (RR'dtc-=N,N-disubstituted dithiocarbamate) and the oxygen atom transfer reactions between [MoO_2 (RR'dtc) _2] and PPh_3 in 1,2-C_2H_4Cl_2 at 25ﾟC are systematically investigated. A good correlation between logarithmic values of second-order rate constants kappa_1 of the oxygen atom transfer reactions and redox potentials EPSILONﾟ' for [MoO_2 (RR'dtc) _2] ^<0/-1> couples is observed over the wide range of kappa_1 (from 0.012 M^<-1>s^<-1> to 0.61 M^<-1>s^<-1>) : the values of log kappa_1 linearly increase with the increase of EPSILONﾟ'. The departure from the correlation line is exactly observed for [MoO_2 (Bz_2dtc) _2] /PPh_3, [MoO_2 (Ph_2dtc) _2] /PPh_3, and [MoO_2 (BzPhdtc) _2] /PPh_3 systems. The anomaly observed for [M … More oO_2 (Bz_2dtc) _2] /PPh_3, [MoO_2 (Ph_2dtc) _2] /PPh_3, and [MoO_2 (BzPhdtc) _2] /PPh_3 seems to be owing to the existence of an aromatic ring behind a sulphur atom cis to two oxo ligands of [MoO_2 (RR'dtc) _2].2) A noble cis-dioxomolybdenum (VI) complex with a quadridentate dithiocarbamato ligand was synthesized and kinetics of oxygen atom transfer reactions between the complex and PPh_3 was investibgated. Oxygen atom transfer reactions between the complex and PPh_3 proceed simply to form a mu-oxomolybdenum (V) dinuclear complex.3) The electrochemical properties of oxomolybdenum (IV) complexes with a several dithiocarbamates were studied. The redcution potentails of the oxomolybdenum (VI) complexes were influenced by the nature of the substituents on the dithiocarbamate ligands, while the oxidation potentials were dependent on the nature of the solvents.4) The electrochemical reduction properties of a series of oxovanadium (IV) complexes with dithiocarbamates were investigated. The pi-interaction between an oxometal center and a thiolate ligand influencing to the reduction potentials of the complexes is stronger in the case of the oxomolybdenum complexes than the oxovanadium complexes. Less

我们研究了含氧钼与1,1-二硫醇盐配合物的氧化还原性质。本研究结果总结如下。1)一系列顺式二氧代(二硫代氨基甲酸酯)钼(VI)配合物[MoO_2(RR)的电化学性质。 'dtc) _2] (RR'dtc-=N,N-二取代系统地研究了25°C下1,2-C_2H_4Cl_2中[MoO_2(RR'dtc)_2]和PPh_3之间的氧原子转移反应的二阶速率常数kappa_1的对数值之间良好的相关性。 [MoO_2 (RR'dtc) 的氧原子转移反应和氧化还原电位 EPSILONﾟ' _2] ^<0/-1> 对在广泛的 kappa_1 范围内（从 0.012 M^<-1>s^<-1> 到 0.61 M^<-1>s^<-1>）观察到： log kappa_1 的值随着 EPSILONﾟ' 的增加而线性增加。 [MoO_2 (Bz_2dtc) _2] 正好观察到与相关线的偏离。 /PPh_3、[MoO_2 (Ph_2dtc) _2] /PPh_3 和 [MoO_2 (BzPhdtc) _2] /PPh_3 系统观察到的异常。 [M … More oO_2 (Bz_2dtc) _2] /PPh_3、[MoO_2 (Ph_2dtc) _2] / PPh_3 和 [MoO_2 (BzPhdtc) _2] /PPh_3 似乎归因于 [MoO_2 (RR'dtc) _2].2) 的两个氧代配体顺式硫原子后面存在芳环。2) 一种高贵的顺式二氧代钼 (VI) 配合物合成了四齿二硫代氨基甲酸酯配体，并分析了该配合物与PPh_3之间氧原子转移反应的动力学配合物与PPh_3之间的氧原子转移反应简单地形成mu-氧代钼(V)双核配合物。3)研究了氧代钼(IV)与几种二硫代氨基甲酸盐配合物的电化学性质。 VI) 配合物受到二硫代氨基甲酸酯配体上取代基性质的影响， 4)研究了一系列氧钒(IV)与二硫代氨基甲酸盐配合物的电化学还原性质，研究了氧代金属中心和硫醇盐配体之间的π相互作用对还原电位的影响。在氧代钼络合物的情况下，络合物的强度比氧钒络合物更强。