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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Tris(pyrazolyl)phosphines with copper(I): from monomers to polymers
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Tris(pyrazolyl)phosphines with copper(I): from monomers to polymers

机译：三（吡唑基）膦与铜（I）：从单体到聚合物

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The parent tris(pyrazolyl) phosphine and its 3,5-Me-2, 3-Ph, and 3-t-Bu derivatives have been prepared by a simple procedure and show modest Lewis basicity of the phosphorus apex as was established by the magnitude of the (1)J(P,Se) coupling constant of the phosphine selenides. Because of the chelating properties of both the N- and P-sites, neutral phosphorus-centered scorpion ligands allow coordination modes that are unavailable to the abundantly used anionic tris(pyrazolyl) borate scorpionates as we established for Cu(I)-complexation. The substituted P-scorpion ligands only allow for N- coordination, as the P-apex is presumably less accessible. Two X-ray crystal structures were obtained for the Cu-complex of tris(3,5-dimethylpyrazolyl)-phosphine with acetonitrile and triphenylphosphine in the fourth coordination site. The parent P-scorpion ligand can chelate with both its pyrazolyl groups and its P-apex with the product depending on the ratio in which it is mixed with the Cu(I) complex. Reacting two equivalents of the ligand with [Cu(MeCN)(4)][PF6] resulted in a complex in which Cu is coordinated to the three pyrazolyl groups of one ligand and to the P-apex of the other ligand as confirmed by an X-ray crystal structure determination and a DFT computational analysis. Reacting the ligand and the Cu(I) complex in an equimolar ratio resulted in a remarkable one-dimensional P-scorpion coordination polymer for which a single crystal X-ray structure could be determined. A detailed analysis of the structural features is presented.
机译：母体三（吡唑基）膦及其3,5-Me-2、3-Ph和3-t-Bu衍生物已通过简单的方法制备，并显示出磷尖的适度的Lewis碱度（由量级确定）硒化膦的（1）J（P，Se）耦合常数由于N和P位的螯合特性，中性的以磷为中心的蝎子配体允许形成配位模式，而配位模式对于我们为Cu（I）络合所建立的阴离子型三（吡唑基）硼酸根阴离子的蝎子而言是不可用的。取代的P-蝎配体仅允许N-配位，因为P-顶点可能难以获得。在第四个配位部位，三（3,5-二甲基吡唑基）膦与乙腈和三苯膦的铜配合物获得了两个X射线晶体结构。取决于其与Cu（I）配合物混合的比例，亲本P-蝎配体可以与吡唑基和其P-顶点与产物螯合。通过[Cu（MeCN）（4）] [PF6]使两当量的配体反应，形成一种络合物，其中Cu与一个配体的三个吡唑基和另一个配体的P-顶点配位，如X射线晶体结构确定和DFT计算分析。使配体和Cu（I）络合物以等摩尔比反应，得到了显着的一维P蝎配位聚合物，可以确定其单晶X射线结构。给出了结构特征的详细分析。

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