膦杂吡唑金属有机及自由基化合物-合成、结构和性能

This project, on the basis of the nature of noninnocent 1,2,4-diazaphospholides, outlines a research plan that is designed to synthesize a series of 1,2,4-diazaphospholide complexes, including planar-chiral complexes, metallodendrimeric complexes, frustrated Lewis pairs, carbene complexes, magnetic coordinated complexes, and persistent dianionic radical complexes. Complexes are both highly potential for the variety of magnetic materials, the organic catalysis, and the fundamentally theoretic interest. The 1,2,4-diazaphospholide ligands containing in the complexes play a key role for the stabilization of the novel species. We seek to maximize the thermal stability of complexes by designing 1,2,4-diazaphospholides with the versatility in donor function and steric demanding. Such an approach represents the ultimate marriage between electronic donor (ligands) and electronic acceptor (metal ions).Recent results have shown that a few 1,2,4-diazaphospholide pseudo-ruthenocences with planar-chirality and a persistent dipotassium dianionic radical complex are potential for the asymmetric catalysis and fundamentally theoretical interest. The electronic structure of the persistent dipotassium dianionic radical complex bearing 1,2,4-diazaphospholides has aroused the general questions of what happens when an electron is added to a five-membered aromatic heterocyclic ring obeying the 4n+2 Huckel rule. Specific objectives include the synthesis of nickel, cobalt, iron, chromium, manganese, copper, ruthenium, palladium, titanium (III), boron, and aluminum 1,2,4-diazaphospholides with varied coordination modes; development of synthetic strategies that lead to planar-chiral complexes, metallodendrimeric complexes, frustrated Lewis pair complexes, carbene complexes, particularly, stable dianionic radical complexes; and concurrent use of molecular orbital calculations to understand bonding and electronic structure in the complexes, especially in dianionic radical complexes. All of the complexes that are prepared in this study will be carefully analyzed with regard to single crystal X-ray diffraction analysis, 1H, 13C{1H}, 31P{1H} NMR, IR, CV, EPR, and elemental analysis. The catalytic beheaviors and magnetic nature of the complexes will be carefully examined in this study by specifically designed organic transformations or by the SQUID method.

膦杂吡唑是一类五元芳香杂环化合物，由于杂环N、P(sp2)原子的协同作用，表现出十分特殊的性质。最近我们发现膦杂吡唑具有两个重要的化学性质：能与金属离子生成平面手性金属有机化合物；作为变价有机分子、与金属离子生成室温下稳定的二负离子自由基金属有机化合物。杂环和低能级LUMO磷原子可能是稳定二负离子自由基金属有机化合物的原因，其存在于分子内双电子库伦排斥力和违反休克尔规则所产生的基本实验和理论问题有待于进一步研究。本申请将根据膦杂吡唑具有变价配体的结构特点，以膦杂吡唑单阴离子和二负离子自由基金属有机化合物前期研究成果为基础，设计合成一系列结构适宜的膦杂吡唑、膦杂吡唑平面手性金属有机化合物、树状金属有机化合物、受阻路易斯酸碱对化合物、卡宾金属有机化合物、特别是二负离子自由基配位下稳定自由基金属有机化合物；系统研究这些金属有机化合物的晶体结构、氧化还原特性、电子结构、催化性能及所涉及的理论问题。

（1）.发明了不对称五元氮膦杂环的合成方法，为平面手性金属有机化合物的合成扫平了道路(Phosphorus, Sulfur, and Silicon and the Related Elements 2014, 189, 1)；.（2）.五元氮膦杂环平面手性不对称钌的夹心化合物的制备已经取得成功。完善性研究工作正在进行中;.（3）.发现并分离出膦杂吡唑中性自由基及其二聚现象(Chem. Commun. 2015, 51, 12680–12683)；.（4）.发现膦杂吡唑自由基参与下的金属还原反应，并得到一系列车轮型含主族Bi–Bi键化合物(Chem. Commun. 2015, 51, 16184–16187);.（5）.发现膦杂吡唑自由基参与下的金属还原反应，并得到一系列车轮型含主族Sb–Sb键化合物(Dalton Trans. 2016, 45, 10505–10509);.（6）.合成了一系列具有新颖结构的膦杂吡唑重稀土金属配合物，并由顺磁共振谱发现了个别化合物的分子内电子转移现象(Dalton Trans. 2016, 45, 899–903);.（7）.合成了一系列膦杂吡唑轻稀土金属配合物，发现了个别化合物的特殊磁现象(Dalton Trans. 2016, 45, 11172–11181);.（8）.合成了一系列新颖的膦杂吡唑碱金属配合物(Organometallics 2014, 33, 6013);.（9）.合成了一个分子离子型化合物，并发现了分子集团在类烯丙基上1,3-迁移现象(Organometallics 2013, 32, 4050);.（10）.合成了一个平面型层状金属钡的三唑聚合物(Inorg. Chim. Acta, 2013, 396, 21);.（11）.合成了一系列新型膦杂吡唑，为推动该领域的进一步发展奠定了基础(J. Mol. Struct. 2014, 1058, 62-70);.（12）.合成了一系列吡唑Ga化合物及含低价Ga-Ga金属键化合物，发现了一个特殊的烯烃插入反应(J. Organomet. Chem. 2015, 780, 1–5);.（13）.合成了几个膦杂吡唑Cr(III)化合物，并研究了它们的宏观磁性和微观磁性(Z. Naturforsch. B. 2016, 71(7), 795–