Maurer Christian, Pittenauer Ernst, Puchberger Michael, Allmaier Günter, Schubert Ulrich
Institute of Materials Chemistry, Vienna University of Technology 1060 Vienna (Austria), E-mail:
Chempluschem. 2013 Apr;78(4):343-351. doi: 10.1002/cplu.201300014. Epub 2013 Feb 27.
The treatment of titanium alkoxides with 1,5-pentanedioxime or 2,5-hexanedioxime resulted in the formation of complexes [{Ti(OR)}] in which the dioximate ligands () bridge a dimeric Ti(μ-OR) unit. The structures of the complexes were determined by single-crystal structure analysis, ESI mass spectrometry, and 1D and 2D solution NMR spectroscopy. In contrast, the treatment of titanium alkoxides with dioximes bearing cyclic linkers, such as cyclohexyl or aryl groups, resulted in insoluble polymeric compounds. The treatment of various bis(salicylaldiminates) with titanium and zirconium alkoxides resulted in compounds with the same composition [{Ti(OR)}], in which, however, two monomeric Ti(OR) units are bridged by the ligands . The two structural possibilities can be distinguished by low-energy collision-induced dissociation owing to their different fragmentation patterns.
用1,5 - 戊二肟或2,5 - 己二肟处理钛醇盐会生成配合物[{Ti(OR)}]，其中二肟酸配体（）桥连一个二聚体Ti(μ-OR)单元。通过单晶结构分析、电喷雾电离质谱以及一维和二维溶液核磁共振光谱确定了配合物的结构。相比之下，用带有环状连接基（如环己基或芳基）的二肟处理钛醇盐会生成不溶性聚合物化合物。用钛和锆醇盐处理各种双（水杨醛亚胺）会生成具有相同组成[{Ti(OR)}]的化合物，然而，其中两个单体Ti(OR)单元由配体桥连。由于它们不同的碎裂模式，这两种结构可能性可以通过低能碰撞诱导解离来区分。
