Baunemann Arne, Kim Younsoo, Winter Manuela, Fischer Roland A
Lehrstuhl für Anorganische Chemie II-Organometallics and Materials Chemistry, Ruhr-University Bochum, Bochum, Germany.
Dalton Trans. 2006 Jan 7(1):121-8. doi: 10.1039/b512074h. Epub 2005 Nov 1.
The coordination chemistry of the hydrazine derivatives dimethylhydrazine (Hdmh) and N-trimethylsilyl-N'N'-dimethylhydrazine (Htdmh) at Ta, Zr and Hf was investigated aiming at volatile mixed ligand all-nitrogen coordinated compounds. The hydrazido ligands were introduced either by salt metathesis employing the Li salts of the hydrazines and the tetrachlorides MCl(4) (M = Zr, Hf) or by amine substitution using M(NR(2))(4) (R = Me, Et) and [(t-BuN)Ta(NR(2))(3)]. The new complexes were fully characterised including (1)H/(13)C NMR, mass spectrometry and a study of their thermal behaviour. The crystal structures of [ZrCl(tdmh)(3)] and the all-nitrogen coordinated complex [Ta(N-t-Bu)(NMe(2))(2)(tdmh)] are discussed as well as the structure of the by-product Li(tdmh)(py). Preliminary MOCVD experiments of the liquid compound [Ta(NEt(2))(2)(N-t-Bu)(tdmh)] were performed and the deposited TaN(Si) films were analysed by RBS and SEM.
为了研究挥发性混合配体全氮配位化合物，对肼衍生物二甲基肼（Hdmh）和N-三甲基硅基-N'N'-二甲基肼（Htdmh）在钽、锆和铪上的配位化学进行了研究。通过使用肼的锂盐和四氯化物MCl₄（M = Zr，Hf）进行盐复分解反应，或使用M(NR₂)₄（R = Me，Et）和[(t-BuN)Ta(NR₂)₃]进行胺取代反应来引入酰肼配体。对新配合物进行了全面表征，包括¹H/¹³C NMR、质谱分析及其热行为研究。讨论了[ZrCl(tdmh)₃]和全氮配位配合物[Ta(N-t-Bu)(NMe₂)₂(tdmh)]的晶体结构，以及副产物[Li(tdmh)(py)]₂的结构。对液态化合物[Ta(NEt₂)₂(N-t-Bu)(tdmh)]进行了初步的金属有机化学气相沉积（MOCVD）实验，并通过卢瑟福背散射（RBS）和扫描电子显微镜（SEM）对沉积的TaN(Si)薄膜进行了分析。
