The synthesis,characterization,and theoretical studies of titanium-μ-N_(2) complexes with di-anionic guanidinate ligands were reported as the first example of its kind.Thus,with(Me_(3)Si)_(2)N-guanidinate ligands,the...The synthesis,characterization,and theoretical studies of titanium-μ-N_(2) complexes with di-anionic guanidinate ligands were reported as the first example of its kind.Thus,with(Me_(3)Si)_(2)N-guanidinate ligands,the mono-anionic guanidinate-supported titanium-μ-N2complex 1 was obtained.Then,reduction of 1 with potassium afforded the di-anionic guanidinate-supported titanium-μ-N_(2) complex 2 via cleavage of one N–Si bond of the(Me3Si)2N substituents in 1,changing the guanidinate ligands automatically from mono-anionic to di-anionic and remarkably lengthening the bond length of theμ-N_(2).Characteristic studies and DFT calculations were performed to reveal that the di-anionic guanidinate ligands stabilized the geometry of 2 and increased the charge density on the bridging dinitrogen.展开更多
A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometr...A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometry,Mössbauer spectroscopy,and elemental analysis.The conversion relationship and the change of the spin states among the iron complexes with different valences were studied in detail.展开更多
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air, the National Natural Science Foundation of China (21988101)supported by the High-performance Computing Platform of Peking University
文摘The synthesis,characterization,and theoretical studies of titanium-μ-N_(2) complexes with di-anionic guanidinate ligands were reported as the first example of its kind.Thus,with(Me_(3)Si)_(2)N-guanidinate ligands,the mono-anionic guanidinate-supported titanium-μ-N2complex 1 was obtained.Then,reduction of 1 with potassium afforded the di-anionic guanidinate-supported titanium-μ-N_(2) complex 2 via cleavage of one N–Si bond of the(Me3Si)2N substituents in 1,changing the guanidinate ligands automatically from mono-anionic to di-anionic and remarkably lengthening the bond length of theμ-N_(2).Characteristic studies and DFT calculations were performed to reveal that the di-anionic guanidinate ligands stabilized the geometry of 2 and increased the charge density on the bridging dinitrogen.
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101).
文摘A series of structurally well-defined iron-dinitrogen complexes(LFe-N2)bearing cyclopentadienylphosphine ligands(L)were synthesized and analyzed by single-crystal X-ray structural analysis,IR/Raman spectra,magnetometry,Mössbauer spectroscopy,and elemental analysis.The conversion relationship and the change of the spin states among the iron complexes with different valences were studied in detail.
