Kinetic study of the oxygen-transfer reactions from the oxo diperoxo complexes of molybdenum(VI) and tungsten(VI) to (thiolato)- and (sulfenato)cobalt(III) complexes
Kinetic study of the oxygen-transfer reactions from the oxo diperoxo complexes of molybdenum(VI) and tungsten(VI) to (thiolato)- and (sulfenato)cobalt(III) complexes
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钼(VI)和钨(VI)的氧代二过氧配合物到(硫醇)-和(磺基)钴(III)配合物的氧转移反应的动力学研究
DOI：
10.1021/ic00299a017
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发表时间：
1988
影响因子：
4.6
通讯作者：
R. Thompson
中科院分区：
文献类型：
--
作者：
A. F. Ghiron;R. Thompson
（硫代）钴（III）配合物（en）{sub 2}Co(SCH{sub 2}CH{sub 2}NH{sub 2}){sup 2+}首先被氧化为（en）{sub 2}Co(S(O)CH{sub 2}CH{sub 2}NH{sub 2}){sup 2+}，然后被Mo（VI）和W（VI）的氧双过氧配合物更慢地氧化为（en）{sub 2}Co(S(O){sub 2}CH{sub 2}CH{sub 2}NH{sub 2}){sup 2+}。几乎定量的氧原子从过氧化物转移到配位硫受体伴随着这些反应。只要有足够的过氧化氢存在以维持氧-双过氧配合物，这些反应对d{sup}金属离子具有严格的催化作用。配位过氧基的活化令人印象深刻；各底物的相对反应活性顺序为WO(O{sub 2}){sub 2} > WO(OH)(O{sub 2}){sub 2}{sup {-}} > MoO(O{sub 2}){sub 2} > MoO(OH)(O{sub 2}){sub 2}{sup {-}} {much gt} H{sub 2}O{sub 2}。测定了除WO(O{sub 2}){sub 2}外所有反应的二阶速率常数和活化参数。这些数据不足以区分配位硫的亲核攻击是直接发生在过氧配体上，还是在Mo（VI）或W（VI）上事先配位。
The (thiolato)cobalt(III) complex (en){sub 2}Co(SCH{sub 2}CH{sub 2}NH{sub 2}){sup 2+} is oxidized first to (en){sub 2}Co(S(O)CH{sub 2}CH{sub 2}NH{sub 2}){sup 2+} and then much more slowly to (en){sub 2}Co(S(O){sub 2}CH{sub 2}CH{sub 2}NH{sub 2}){sup 2+} by the oxo diperoxo complexes of Mo(VI) and W(VI). Nearly quantitative oxygen atom transfer from peroxide to the coordinated sulfur acceptor accompanies these reactions. The reactions are strictly catalytic with respect to the d{sup o} metal ions, provided sufficient hydrogen peroxide is present to maintain them as oxo diperoxox complexes. The activation of the coordinated peroxo group is impressive; the relative reactivities for each substrate stand in the order WO(O{sub 2}){sub 2} > WO(OH)(O{sub 2}){sub 2}{sup {minus}} > MoO(O{sub 2}){sub 2} > MoO(OH)(O{sub 2}){sub 2}{sup {minus}} {much gt} H{sub 2}O{sub 2}. Second-order rate constants and, with the exception of those for WO(O{sub 2}){sub 2}, activation parameters for all these reactions were determined. The data are insufficient to distinguish whether nucleophilic attack by coordinated sulfur occurs directly at the peroxo ligand or after prior coordination at Mo(VI) or W(VI).