Transamination Reactivity of Ti(NMe2)4 and Zr(NMe2)4 with 1,3,4,5,6-Pentamethyl-2-aminoborazine and Aryl Amines. Model Chemistry for the Formation of Metalloborazine Preceramic Polymers and MN/BN (M?=?Ti, Zr) Ceramic Composites |
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| Authors: | Maomin Fan Eileen N Duesler Jerzy F Janik and Robert T Paine |
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| Affiliation: | (1) Department of Chemistry, University of New Mexico, Albuquerque, NM 87131, USA;(2) Faculty of Fuels and Energy, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow, Poland |
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| Abstract: | The transamination reactions between Ti(NMe2)4 and 1,3,4,5,6-pentamethyl-2-aminoborazine, (Me)3N3(Me)2B3(NH2), and diphenylamine (Ph2NH) and between Zr(NMe2)4]2 and 1,3,4,5,6-pentamethyl-2-aminoborazine, aniline (PhNH2) and diphenylamine have been studied and the molecular product species have been isolated, spectroscopically characterized
and single crystal X-ray structure analyses completed. The results of these studies have been used to interpret the outcome
of reactions of Ti(NMe2)4 and Zr(NMe2)4 with borazinylamine preceramic polymers that, upon pyrolysis, produce TiN/BN, ZrN/BN and ZrH0.6N/BN composite powders.
The transamination reactivity of a two-point poly(borazinylamine) oligomer having terminal –NH2 amino groups with Ti(NMe2)4 and Zr(NMe2)4 has been used to obtain metallated preceramic oligomers that, upon pyrolysis, give TiN/BN and ZrN/ZrH0.6N/BN nanocomposites. Model reactions of 1,3,4,5,6-pentamethyl-2-amino borazine, aniline and Ph2NH2 with Ti(NMe2)4 and Zr(NMe2)4 are also described as models for the formation of the metallated oligomers. Molecular structure determinations for the metal
amides are presented.
We dedicate this paper to Professor Christopher W. Allen in recognition of his distinguished career and his accomplishments
in inorganic ring and polymer chemistry. |
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| Keywords: | Titanium amides zirconium amides titanium nitride zirconium nitride boron nitride composites X-ray crystallography |
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