Transamination Reactivity of Ti(NMe 2 ) 4 and Zr(NMe 2 ) 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 Maomin Fan, 1 Eileen N. Duesler, 1 Jerzy F. Janik, 1,2 and Robert T. Paine 1,3 Submitted July 31, 2006; Accepted September 26, 2006 The transamination reactions between Ti(NMe 2 ) 4 and 1,3,4,5,6-pentamethyl-2-aminobor- azine, (Me) 3 N 3 (Me) 2 B 3 (NH 2 ), and diphenylamine (Ph 2 NH) and between [Zr(NMe 2 ) 4 ] 2 and 1,3,4,5,6-pentamethyl-2-aminoborazine, aniline (PhNH 2 ) 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(NMe 2 ) 4 and Zr(NMe 2 ) 4 with borazinylamine preceramic polymers that, upon pyrolysis, produce TiN/BN, ZrN/BN and ZrH 0.6 N/BN composite powders. KEY WORDS: Titanium amides; zirconium amides; titanium nitride; zirconium nitride; boron nitride composites; X-ray crystallography 1. INTRODUCTION A large variety of inorganic polymers have been employed as precursor reagents for the formation of binary non-oxide e.g., boride, carbide, nitride and silicide, ceramic compositions [1, 2]. The organic polymer-like processibility of these preceramic poly- mers makes it possible to obtain the ceramic materials in technologically useful forms including near-net shape bodies, fibers, coatings, xerogels and aerogels [1–6]. In recent years, with the discovery of increas- ingly complex polymer compositions, it has also become possible to access ternary and quanternary ceramic compositions with near continuous combin- ing ratios. This allows for considerable flexibility in achieving finished ceramic materials with designed performance properties. Prior work from our group has shown that poly(borazinylamines) are readily formed in solution reactions of appropriate borazine monomers with disilazane reagents [7–18]. Depending upon the specific borazine monomer, the disilazane coupling agent and the polymer processing steps employed, numerous preceramic polymers are obtained with a range of chemical reactivities built into the structures. Generalized structures for so-called three-point (1) and two-point (2) polymer structures are shown here. In 1, the borazine monomer rings are coupled via We dedicate this paper to Professor Christopher W. Allen in recognition of his distinguished career and his accomplishments in inorganic ring and polymer chemistry. 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. 3 To whom correspondence should be addressed. E-mail: rtpaine@unm.edu Journal of Inorganic and Organometallic Polymers and Materials, Vol. 17, No. 2, June 2007 (Ó 2007) DOI: 10.1007/s10904-007-9125-4 423 1574-1443/07/0600-0423/0 Ó 2007 Springer Science+Business Media, LLC