| Project/Area Number |
07640734
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Yamagata University |
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Principal Investigator |
UNOURA Kei Yamagata University, Department of Material and Biological Chemistry, Associate Professor, 理学部, 助教授 (20151920)
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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1996: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1995: ¥1,700,000 (Direct Cost: ¥1,700,000)
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| Keywords | OXOMOLYBDENUM COMPLEXES / 1,1-DITHIOLATES / ELECTROCHEMISTRY / OXYGEN ATOM TRANSFER / KINETICS / OXOVANADIUM COMPLEXES |
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| Research Abstract |
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
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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
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