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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Mono, bis, and tris(phosphoramidate) titanium complexes: synthesis, structure, and reactivity investigations
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Mono, bis, and tris(phosphoramidate) titanium complexes: synthesis, structure, and reactivity investigations

机译：单体，BIS和TRIS（磷酸氨基酯）钛配合物：合成，结构和反应性研究

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摘要

A series of variously substituted phosphoramidate titanium complexes bearing dimethylamido ligands are reported. Aryl-substituted ligands impart crystallinity to the systems and allow for the elucidation of the molecular structures via X-ray crystallography. Higher-substituted complexes, including a tris(phosphoramidate)mono(dimethylamido) complex, were isolated and characterized in the solid state, as well as in solution using variable temperature H-1 and P-31 NMR spectroscopy. The steric bulk possessed by this ligand system, relative to amidate and ureate ligands, has allowed access to a mono(phosphoramidate)tris(dimethylamido) complex. The first solid-state-molecular structure of a mono-ligated 1,3-N,O chelated complex of titanium is reported and compared to the respective bis- and tris-analogues. These complexes were screened for hydroaminoalkylation activity between secondary amines and terminal alkenes and the intramolecular hydroamination of a terminal aminoalkene. Mono(phosphoramidate)tris(dimethylamido) complexes were screened in situ and found to be more active than their respective bis(N,O)-chelated analogues. The elucidation of these complexes allows for a direct comparison to other N,O-chelates of early transition metals, particularly in their hydroaminoalkylation and hydroamination reactivity.
机译：报道了一系列不同的取代氨基甲酸钛配合物，其含有二甲基氨基配体。芳基取代的配体赋予系统的结晶度并允许通过X射线晶体学阐明分子结构。将包括TRIS（磷酸酯）单体（二甲基氨基）复合物的更高取代的络合物分离和以固态分离，以及使用可变温度H-1和P-31 NMR光谱的溶液中。该配体系统具有相对于酰胺和尿酸配体具有的空块，使得允许获得单体（磷酸氨基酯）三（二甲基氨基）复合物。报告并与各自的双和三 - 类似物相比，据报道了一种单连接的1,3-N，O螯合络合物的第一固态分子结构。将这些配合物筛选用于仲胺和末端烯烃之间的羟氨基烷基化活性和末端氨基烷烃的分子内的水中。原位筛选单体（磷酸氨基酯）三（二甲基氨基）复合物，发现比它们各自的双（n，o）水化类似物更有效。这些配合物的阐明允许与早期过渡金属的其他N，O形螯合物直接比较，特别是在其水氨基烷基化和水醋酸反应性中。

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