Baunemann Arne, Hellwig Malte, Varade Ashish, Bhakta Raghunandan K, Winter Manuela, Shivashankar S A, Fischer Roland A, Devi Anjana
Lehrstuhl für Anorganische Chemie II, Universitätsstr. 150, Ruhr-University Bochum, Bochum, 44780, Germany.
Dalton Trans. 2006 Jul 28(28):3485-90. doi: 10.1039/b601995a. Epub 2006 Apr 27.
Novel mixed amido-malonato complexes of titanium are reported. The complexes were synthesized by partially replacing the amido groups from the complexes [Ti(NMe2)4] and [Ti(NEt2)4] via Brønstedt acid/base reactions, using the malonate-ligands di-isopropylmalonate (Hdpml) and di-tert-butylmalonate (Hdbml). Four representative complexes were synthesized and fully characterised by 1H NMR, 13C NMR, CHN analysis and mass spectrometry. The crystal structures of the six-coordinated complexes [Ti(NMe2)2(dbml)2] (3) and [Ti(NEt2)2(dbml)2] (4) are presented and discussed. The complexes are solids and the chemical and thermal characteristics of the complexes strongly depend on the substitution at the malonate ligand. While dpml containing complexes show a promising behaviour for classical MOCVD, dbml containing complexes seem to be more suitable for liquid injection-metal-organic chemical vapour deposition (LI-MOCVD). Based on its thermal characteristics, the most promising complex for thermal CVD, [Ti(NEt2)2(dpml)2] (2) was selected for preliminary MOCVD experiments, which indicate a good suitability for the deposition of TiO2 thin films.
报道了新型钛的混合酰胺基丙二酸酯配合物。通过布朗斯特酸碱反应，利用丙二酸酯配体二异丙基丙二酸酯（Hdpml）和二叔丁基丙二酸酯（Hdbml），部分取代配合物[Ti(NMe2)4]和[Ti(NEt2)4]中的酰胺基，合成了这些配合物。合成了四种代表性配合物，并通过1H NMR、13C NMR、CHN分析和质谱对其进行了全面表征。给出并讨论了六配位配合物[Ti(NMe2)2(dbml)2]（3）和[Ti(NEt2)2(dbml)2]（4）的晶体结构。这些配合物为固体，其化学和热性质强烈依赖于丙二酸酯配体上的取代基。含dpml的配合物在传统金属有机化学气相沉积（MOCVD）中表现出良好的性能，而含dbml的配合物似乎更适合于液体注入金属有机化学气相沉积（LI-MOCVD）。基于其热性质，选择了最有前景的用于热化学气相沉积（CVD）的配合物[Ti(NEt2)2(dpml)2]（2）进行初步的MOCVD实验，结果表明其对TiO2薄膜的沉积具有良好的适用性。
