Synthesis and Structure of a Novel Lewis Acid-Base Adduct, (H(3)C)(3)SiN(3).GaCl(3), en Route to Cl(2)GaN(3) and Its Derivatives: Inorganic Precursors to Heteroepitaxial GaN.

The formation of a novel Lewis acid-base complex between the silyl azide Si(CH(3))(3)N(3) and GaCl(3) having the formula (H(3)C)(3)SiN(3).GaCl(3)()()(1) is demonstrated. The X-ray crystal structure of 1 shows that the electron-donating site is the nitrogen atom directly bonded to the organometallic group. Compound 1 crystallizes in the orthorhombic space group Pnma, with cell dimensions a = 15.823(10) Å, b = 10.010(5) Å, c = 7.403(3) Å, and Z = 4. Low-temperature decomposition of 1 via loss of (H(3)C)(3)SiCl yields Cl(2)GaN(3) (2), which serves as the first totally inorganic (C,H-free) precursor to heteroepitaxial GaN by ultrahigh-vacuum chemical vapor deposition. A volatile monomeric Lewis acid-base adduct of 2 with trimethylamine, Cl(2)GaN(3).N(CH(3))(3) (3), has also been prepared and utilized to grow high-quality GaN on Si and basal plane sapphire substrates. The valence bond model is used to analyze bond lengths in organometallic azides and related adducts.