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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.
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页码:21784 / 21788
页数:5
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