Gallium and Indium Hydrazides. Molecular and Electronic Structure of In[N(SiMe3)NMe2]3 and Related Compounds

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Gallium and indium hydrazides, Ga[N(SiMe(3))NMe(2)](3) (1) and In[N(SiMe(3))NMe(2)](3) (2), were synthesized from the reactions of metal chlorides and Li[N(SiMe(3))NMe(2)]. 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[bond]N distance of 2.078(3) A and the N[bond]In[bond]N[bond]N dihedral angles did not provide clear structural evidence of In[bond]N pi-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(SiMe(3))(2)](3) (3) and In[N((t)Bu)(SiMe(3))](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 pi-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 beta-nitrogens of the hydrazido ligands with the HOMO of the InN(3) core.