Saly Mark J, Heeg Mary Jane, Winter Charles H
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
Inorg Chem. 2009 Jun 15;48(12):5303-12. doi: 10.1021/ic900342j.
Treatment of MI(2) (M = Ca, Sr) or BaI(2)(THF)(3) with 2 equiv of potassium tris(3,5-diethylpyrazolyl)borate (KTp(Et2)) or potassium tris(3,5-di-n-propylpyrazolyl)borate (KTp(nPr2)) in hexane at ambient temperature afforded CaTp(Et2)(2) (64%), SrTp(Et2)(2) (64%), BaTp(Et2)(2) (67%), CaTp(nPr2)(2) (51%), SrTp(nPr2)(2) (75%), and BaTp(nPr2)(2) (39%). Crystal structure determinations of CaTp(Et2)(2), SrTp(Et2)(2), and BaTp(Et2)(2) revealed monomeric structures. X-ray structural determinations for strontium tris(pyrazolyl)borate (SrTp(2)) and barium tris(pyrazolyl)borate (BaTp(2)) show that SrTp(2) exists as a monomer and BaTp(2) exists as a dimer containing two bridging Tp ligands. The thermogravimetric analysis traces, preparative sublimations, and melting point/decomposition determinations demonstrate generally very high thermal stabilities and reasonable volatilities. SrTp(2) has the highest volatility with a sublimation temperature of 200 degrees C/0.05 Torr. BaTp(2) is the least thermally stable with a decomposition temperature of 330 degrees C and a percent residue of 46.5% at 450 degrees C in the thermogravimetric analysis trace. SrTp(Et2)(2), BaTp(Et2)(2), CaTp(nPr2)(2), SrTp(nPr2)(2), and BaTp(nPr2)(2) vaporize as liquids between 210 and 240 degrees C at 0.05 Torr. BaTp(Et2)(2) and BaTp(nPr2)(2) decompose at about 375 degrees C, whereas MTp(Et2)(2) and MTp(nPr2)(2) (M = Ca, Sr) are stable to >400 degrees C. Several of these new complexes represent promising precursors for chemical vapor deposition and atomic layer deposition film growth techniques.
在室温下，将MI₂（M = Ca、Sr）或BaI₂(THF)₃与2当量的三（3,5 - 二乙基吡唑基）硼酸钾（KTp(Et₂)）或三（3,5 - 二正丙基吡唑基）硼酸钾（KTp(nPr₂)）在己烷中反应，得到CaTp(Et₂)₂（64%）、SrTp(Et₂)₂（64%）、BaTp(Et₂)₂（67%）、CaTp(nPr₂)₂（51%）、SrTp(nPr₂)₂（75%）和BaTp(nPr₂)₂（39%）。CaTp(Et₂)₂、SrTp(Et₂)₂和BaTp(Et₂)₂的晶体结构测定显示为单体结构。三（吡唑基）硼酸锶（SrTp₂）和三（吡唑基）硼酸钡（[BaTp₂]₂）的X射线结构测定表明，SrTp₂以单体形式存在，[BaTp₂]₂以含有两个桥连Tp配体的二聚体形式存在。热重分析曲线、制备升华以及熔点/分解测定表明，这些化合物通常具有非常高的热稳定性和合理的挥发性。SrTp₂的挥发性最高，升华温度为200℃/0.05 Torr。[BaTp₂]₂的热稳定性最低，在热重分析曲线中，其分解温度为330℃，在450℃时的残留百分比为46.5%。SrTp(Et₂)₂、BaTp(Et₂)₂、CaTp(nPr₂)₂、SrTp(nPr₂)₂和BaTp(nPr₂)₂在0.05 Torr下于210至240℃之间以液体形式汽化。BaTp(Et₂)₂和BaTp(nPr₂)₂在约375℃分解，而MTp(Et₂)₂和MTp(nPr₂)₂（M = Ca、Sr）在高于400℃时稳定。这些新配合物中的几种代表了用于化学气相沉积和原子层沉积薄膜生长技术的有前景的前驱体。
