Reversible and Irreversible [2+2] Cycloaddition Reactions of Heteroallenes to a Gallaphosphene

被引:25
作者
Sharma, Mahendra K. [1 ,2 ]
Wolper, Christoph [1 ,2 ]
Haberhauer, Gebhard [3 ]
Schulz, Stephan [1 ,2 ]
机构
[1] Univ Duisburg Essen, Inst Inorgan Chem, Univ Str 5-7, D-45141 Essen, Germany
[2] Univ Duisburg Essen, Ctr Nanointegrat Duisburg Essen CENIDE, Univ Str 5-7, D-45141 Essen, Germany
[3] Univ Duisburg Essen, Inst Organ Chem, Univ Str 5-7, D-45141 Essen, Germany
关键词
2+2] cycloaddition reactions; CO2; activation; gallaphosphene; heteroallenes; main group elements; N-HETEROCYCLIC CARBENE; CARBON-DIOXIDE BINDING; MAIN-GROUP ELEMENTS; C-H ACTIVATION; MONOMERIC IMIDES; GALLIUM; REACTIVITY; ETHYLENE; BOND; GA;
D O I
10.1002/anie.202108370
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
[2+2] Cycloaddition reactions of gallaphosphene L(Cl)GaPGaL 1 (L=HC[C(Me)N(2,6-i-Pr2C6H3)](2)) with carbodiimides [C(NR)(2); R=i-Pr, Cy] and isocyanates [RNCO; R=Et, i-Pr, Cy] yielded four-membered metallaheterocycles LGa(Cl)P[mu-C(X)NR]GaL (X=NR, R=i-Pr 2, Cy 3; X=O, R=Et 4, i-Pr 5, Cy 6). Compounds 4-6 reversibly react with CO2 via [2+2] cycloaddition at ambient temperature to the six-membered metallaheterocycles LGa(Cl)P[mu-C(O)O]-mu-C(O)N(R)GaL (R=Et 7, i-Pr 8, Cy 9). Compounds 2-9 were characterized by IR and heteronuclear (H-1, C-13{H-1}, P-31{H-1}) NMR spectroscopy and elemental analysis, while quantum chemical calculations provided a deeper understanding on the energetics of the reactions.
引用
收藏
页码:21784 / 21788
页数:5
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