Coordination Compounds of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-Oxide (DOPO) Ligands: Extremely High Thermostability and Ligand Oxidation in the Solid State
Coordination Compounds of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-Oxide (DOPO) Ligands: Extremely High Thermostability and Ligand Oxidation in the Solid State
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DOI：
10.1002/ejic.202000269
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发表时间：
2020-06-23
影响因子：
2.3
通讯作者：
Doering, Manfred
中科院分区：
文献类型：
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作者：
Goedderz, Daniela;Schaefer, Timmy;Doering, Manfred
通过与DOPO和DOPO-OH的钠盐进行盐复分解反应，得到不同的金属次膦酸盐和含锌、钙、镁阳离子的膦酸盐。合成的配合物[Zn(DOPO)(2)](n)、[Zn(DOPO-OH)(2)](n)和[Ca(DOPO)(2)(H2O)](n)具有聚合结构。开环金属次膦酸盐配位化合物[Zn(DOPO)(2)](n)能够进行不可逆的热诱导氧化环化，生成相应的金属膦酸盐[Zn(DOPO-OH)(2)](n)。次膦酸镁和次膦酸钙不能被氧化成其相应的金属膦酸盐络合物。所有有机磷化合物均通过 X 射线晶体学、NMR、TGA 和 TDMS 进行分析。用DSC研究了[Zn(DOPO)(2)](n)的氧化环化反应。此外，通过添加N-甲基咪唑等氮配体，配位聚合物[Zn(DOPO)(2)](n)可以转化为分子配合物，从而使膦酸配体从桥连配体转变为单齿配体。合成的配位化合物表现出高达 520 摄氏度的极高热稳定性。
Different metal phosphinates and phosphonates were obtained containing zinc, calcium and magnesium as cations by means of a salt metathesis reaction with sodium salts of DOPO and DOPO-OH. The synthesized complexes [Zn(DOPO)(2)](n), [Zn(DOPO-OH)(2)](n)and [Ca(DOPO)(2)(H2O)](n)are featured a polymeric structure. The open-ring metal phosphinate coordination compound [Zn(DOPO)(2)](n)is able to undergo a non-reversible thermally induced oxidative cyclisation to the corresponding metal phosphonate [Zn(DOPO-OH)(2)](n). The magnesium and calcium phosphinates cannot be oxidized to their corresponding metal phosphonate complexes. All organophosphorus compounds were analyzed by means of X-ray crystallography, NMR, TGA and TDMS. The oxidative cyclisation reaction of [Zn(DOPO)(2)](n)was investigated by DSC. Additionally, the coordination polymer [Zn(DOPO)(2)](n)can be transformed into a molecular complex by adding nitrogen ligands such asN-methylimidazole, whereby the phosphonate ligand changes from a bridging to a monodentate ligand. The synthesized coordination compounds exhibit very high thermostabilities of up to 520 degrees C.