期刊
INORGANIC CHEMISTRY
卷 61, 期 3, 页码 1270-1274出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03753
关键词
-
资金
- Alexander von Humboldt Foundation
- National Science Foundation [CHE-1955612]
In this study, further reactivity studies of the N(3)PA molecule were conducted, including strain-promoted 1,3-dipolar cycloaddition with cyclooctyne and Staudinger-type reactivity. The click reaction was found to be faster than the dissociation of N(3)PA. The Staudinger-type reactivity allowed transfer of the NPA fragment to a base-stabilized silylene.
11-Azido-9,10-dihydro-9,10-phosphanoanthracene (N(3)PA) has been demonstrated recently as a transfer reagent for molecular phosphorus mononitride (PN) because it easily dissociates at room temperature into dinitrogen (N-2), PN, and anthracene (A). Here we report further reactivity studies of the N(3)PA molecule including strain-promoted 1,3-dipolar cycloaddition with cyclooctyne and Staudinger-type reactivity. Calculations at the DLPNO-CCSD(T)/cc-pVTZ//PBE0-D3(BJ)/cc-pVTZ level of theory indicate that the click reaction is faster than the dissociation of N(3)PA. The Staudinger-type reactivity enabled transfer of the NPA fragment to a base-stabilized silylene. The previously reported intermediate of vanadium trisanilide with an NPA ligand could be isolated in 61% yield and structurally characterized in a single-crystal X-ray diffraction experiment. In line with the previously reported phosphinidene reactivity of the transient vanadium phosphorus mononitride complex, thermolysis or irradiation of the complex leads to A elimination and formation of the corresponding vanadium PN dimer or trimer, respectively.
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