Revisiting the Synthesis and Nucleophilic Reactivity of an Anionic Copper Superoxide Complex

被引：31
作者：
Bailey, Wilson D. [1 ]
Gagnon, Nicole L. [2 ,3 ]
Elwell, Courtney E. [2 ,3 ]
Cramblit, Anna C. [2 ,3 ]
Bouchey, Caitlin J. [1 ,2 ,3 ]
Tolman, William B. [1 ,2 ,3 ]
机构：
[1] Washington Univ, Dept Chem, One Brookings Dr,Campus Box 1134, St Louis, MO 63130 USA
[2] Univ Minnesota, Dept Chem, 207 Pleasant St SE, Minneapolis, MN 55455 USA
[3] Univ Minnesota, Ctr Met Biocatalysis, 207 Pleasant St SE, Minneapolis, MN 55455 USA
来源：
INORGANIC CHEMISTRY | 2019年 / 58卷 / 08期
关键词：
CRYSTAL;
D O I：
10.1021/acs.inorgchem.9b00090
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The addition of 1 equiv of KO2 and Kryptofix222 (Krypt) in CH3CN to a solution of LCu(CH3CN) EL = N,N'-bis(2,6-diisopropylphenyl)2,6-pyridinecarboxamide] in tetrahydrofuran at -80 degrees C yielded [K(Krypt)][LCuO2], the enhanced stability of which enabled reexamination of its reactivity with 2-phenylpropionaldehyde (2-PPA). Mechanistic and product analysis studies revealed that [K(Krypt)] [LCuO2] reacts with wet 2-PPA to form [LCuOH](-), which then deprotonates 2-PPA to yield the copper(II) enolate complex [LCu(OC=C(Me)Ph)](-). Acetophenone was observed upon workup of this complex or mixtures of KO2 and 2-PPA alone, in support of an alternative mechanism(s) to the one proposed previously involving an initial nucleophilic attack at the carbonyl group of 2-PPA.
引用
收藏
页码：4706 / 4711
页数：6
相关论文
共 68 条
[41]  
2017, J BIOL INORG CHEM, V22, P1029, DOI DOI 10.1007/S00775-017-1480-1
[42]  
2003, J AM CHEM SOC, V125, P8974, DOI DOI 10.1021/JA035983P
[43]  
1990, INORG CHEM, V29, P775
[44]  
2017, CHEM REV, V117, P2059, DOI DOI 10.1021/ACS.CHEMREV.6B00636
[45]  
1999, DALTON T, P4511
[46]  
2017, DALTON T, V46, P5965, DOI DOI 10.1039/C7DT00339K
[47]  
1971, J AM CHEM SOC, V93, P4605
[48]  
2003, J AM CHEM SOC, V125, P5644, DOI DOI 10.1021/JA034993N
[49]  
1997, CAN J CHEM, V75, P499
[50]  
2014, CHEM REV, V114, P3659, DOI DOI 10.1021/CR400327T
1234567