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Reactivity of ZrCl4 and HfCl4 with silylamines and thermal decomposition of the compounds [MCl4{NH(R)(SiR′3)}] (M = Zr,Hf, R = tBu,R′ = Me; R = SiR′3 = SiMe3, SiMe2H)
Authors:Plaboni Hasan  Stephen E Potts  Claire J Carmalt  Robert G Palgrave  Hywel O Davies
Institution:1. Department of Chemistry, Christopher Ingold Laboratories, University College London, 20 Gordon Street, London WC1H OAJ, UK;2. SAFC Hitech, Power Road, Bromborough, Wirral CH62 3QF, UK
Abstract:The Lewis acid/base adducts MCl4{NH(R)(SiR′3)}] (M = Zr, Hf; R = tBu, R′ = Me; R = SiR′3 = SiMe3, SiMe2H) were synthesized by the 1:1 reaction of MCl4 with NH(R)(SiR′3) in dichloromethane solution at room temperature. The decomposition of MCl4{NH(R)(SiR′3)}] proceeds with the elimination of R′3SiCl, as shown by thermogravimetric analysis. Pyrolysis of the compounds at 620 °C under inert conditions (N2, vacuum) afforded powders of composition ClMN] or Cl2MNH]. Preliminary low pressure chemical vapour deposition experiments show that MCl4{NH(R)(SiR′3)}] deposits thin films of metal nitride contaminated with metal oxide.
Keywords:Zirconium nitride  Hafnium nitride  Thin film  CVD
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