The tungsten aminoalkoxides W(O)(OPri)3L [L = dmae, OCH2CH2NMe2 (1); bdmap, OCH(CH 2NMe2)2 (2); tdmap, OC(CH2NMe 2)3 (3)] have been synthesised. Controlled hydrolysis of 1-3 has allowed isolation of W4O4(μ-O) 6(dmae)4 (4), W4O4(μ-O) 4(OPri)4(bdmap)4 (5), W 6O6(μ-O)9(tdmap)6 (6), W 4O4(μ-O)6(tdmap)4 (7), W 4O4(μ-O)6(tdmap)4·4H 2O (7a), all of which have been characterised by X-ray crystallography. 4, 7, 7a each embody a W4O6 core with adamantane structure, 5 incorporates a folded W4O4 square and 6 has a trigonal prismatic W6O9 at its heart. 7 decomposes in air at to give orthorhombic WO3, while 1-3 decomposed under an autogenerated pressure (Reaction under Autogenic Pressure at Elevated Temperatures, RAPET) to form mixtures of carbon-coated WOx needles and carbon spherules.
ASJC Scopus subject areas
- Inorganic Chemistry