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- W2002008227 abstract "Gallium and indium hydrazides, Ga[N(SiMe3)NMe2]3 (1) and In[N(SiMe3)NMe2]3 (2), were synthesized from the reactions of metal chlorides and Li[N(SiMe3)NMe2]. Single crystal X-ray crystallographic analysis revealed that compound 2 was monomeric with trigonal planar geometries on the indium and the indium-bonded nitrogen atoms. The average In−N bond distance of 2.078(3) Å and the N−In−N−N dihedral angles did not provide clear structural evidence of In−N π-bonding. The electronic absorption spectra of the indium hydrazido complex revealed transitions at significantly lower energies compared to those observed in the tris(amido) compounds, In[N(SiMe3)2]3 (3) and In[N(tBu)(SiMe3)]3 (4). The absorptions of the indium and gallium compounds were attributed to ligand−metal charge transfer transitions. Trends in the electronic transitions for compounds 2 and 3 calculated at the time-dependent density functional and configuration interaction including single excitations levels, both using a minimal basis set, were consistent with the experimental data, and Mulliken charge analyses support the assignment to ligand-to-metal charge transfer transitions. These calculations also demonstrated the presence of π-bonding between the In and N p-orbitals, and an analogy is drawn to the frontier molecular orbitals of trimethylenemethane. The low-lying spectroscopic transition in 2, and thus its yellow color, results from mixing of the lone pair electrons on the β-nitrogens of the hydrazido ligands with the HOMO of the InN3 core." @default.
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- W2002008227 date "2003-05-03" @default.
- W2002008227 modified "2023-09-27" @default.
- W2002008227 title "Gallium and Indium Hydrazides. Molecular and Electronic Structure of In[N(SiMe<sub>3</sub>)NMe<sub>2</sub>]<sub>3</sub> and Related Compounds" @default.
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- W2002008227 doi "https://doi.org/10.1021/ic020693f" @default.
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