期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 69, 页码 17351-17360出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202103151
关键词
bond activations; carbene complexes; metal ligand cooperativity; reaction mechanisms; structure elucidation
资金
- RESOLV - Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy [EXC-2033, 390677874]
- DFG [DA 1402/6-1]
- Fonds der Chemischen Industrie
- Projekt DEAL
The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P-H bonds has been reported. These complexes exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Additionally, deuteration experiments and computational studies have shown that cyclometallation is initiated at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates.
The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P-H bonds is reported. Complexes of type [(p-cymene)-RuC(SO2Ph)(PPh2NR)] (with R = SiMe3 or 4-C6H4-NO2) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron-rich silyl-substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P-H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron-withdrawing 4-nitrophenyl substituent allowed the selective cooperative P-H activation to form stable activation products.
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