含有双（吡唑-1-基）乙酸酯和双（吡唑-1-基）磺酸酯作为三脚架型N，N，O-杂环螯合配体的新型铼（V）氧配合物。

Novel rhenium(V) oxo complexes containing bis(pyrazol-1-yl)acetate and bis(pyrazol-1-yl) sulfonate as tripodal N,N,O-heteroscorpionate ligands.

作者信息

Porchia Marina, Papini Grazia, Santini Carlo, Gioia Lobbia Giancarlo, Pellei Maura, Tisato Francesco, Bandoli Giuliano, Dolmella Alessandro

机构信息

Department of Chemical Sciences, University of Camerino, Via S. Agostino 1, 62032 Camerino (MC), Italy.

出版信息

Inorg Chem. 2005 May 30;44(11):4045-54. doi: 10.1021/ic050193x.

DOI:10.1021/ic050193x

PMID:15907134

Abstract

Reactions of [NBu4][Re(O)Cl4] with bis(pyrazol-1-yl)methane (bpzm) and bis(pyrazol-1-yl)acetate (Hbpza) and with the lithium salts lithium [bis(3,5-dimethylpyrazol-1-yl)acetate] (Libdmpza) and lithium [bis(3,5-dimethylpyrazol-1-yl)methanesulfonate] (Libdmpzs) produce a series of new compounds containing either a kappa2-N,N bidentate pyrazolyl ligand [Re(O)(bpzm)Cl3 (1), Re(O)(bpzm)(OMe)Cl2 (2), Re(O)(bpzaOMe)(OMe)Cl2 (4)] or a kappa3-N,N,O heteroscorpionate [Re(O)(bpza)Cl2 (3), Re(O)(bdmpza)Cl2 isomers 5 and 6, Re(O)(bdmpza)(OMe)Cl (7), Re(O)(bdmpza)(OEt)Cl (8), Re(O)(bdmpzs)(OMe)Cl (9), Re(O)(bdmpzs)(OEt)Cl (10)]. X-ray analyses of 1 and 3 show in both cases a distorted octahedral environment around the rhenium atom. The nature and the geometry of the products are strongly determined by the reaction solvent and by the heteroscorpionate ligand itself. When scorpionates bear methylated pyrazolyl rings mixed heterocomplexes Re(O)(bdmpza)(glycol) (11) and Re(O)(bdmpzs)(glycol) (12) are obtained (H2glycol = ethylene glycol). Also 11 shows an octahedral geometry as assessed by X-ray study.

摘要

[四丁基铵][高铼酰氯四氯合物][NBu4][Re(O)Cl4]与双(吡唑-1-基)甲烷(bpzm)、双(吡唑-1-基)乙酸(Hbpza)以及锂盐双(3,5-二甲基吡唑-1-基)乙酸锂(Libdmpza)和双(3,5-二甲基吡唑-1-基)甲磺酸锂(Libdmpzs)反应，生成了一系列新化合物，这些化合物含有κ2-N,N双齿吡唑基配体[Re(O)(bpzm)Cl3 (1)、Re(O)(bpzm)(OMe)Cl2 (2)、Re(O)(bpzaOMe)(OMe)Cl2 (4)]或κ3-N,N,O杂螯合配体[Re(O)(bpza)Cl2 (3)、Re(O)(bdmpza)Cl2异构体5和6、Re(O)(bdmpza)(OMe)Cl (7)、Re(O)(bdmpza)(OEt)Cl (8)、Re(O)(bdmpzs)(OMe)Cl (9)、Re(O)(bdmpzs)(OEt)Cl (10)]。对1和3的X射线分析表明，在这两种情况下铼原子周围的环境都是扭曲的八面体。产物的性质和几何结构在很大程度上由反应溶剂和杂螯合配体本身决定。当螯合配体带有甲基化的吡唑环时，会得到混合杂合物Re(O)(bdmpza)(二醇)(11)和Re(O)(bdmpzs)(二醇)(12)(H2二醇 = 乙二醇)。同样，通过X射线研究评估，11也显示出八面体几何结构。