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含碲亚氨基二膦酸酯配体的锡(II)和铅(II)配合物的合成、结构和多核 NMR 谱:从单源前体制备两种形态的纯 PbTe

Synthesis, structures, and multinuclear NMR spectra of tin(II) and lead(II) complexes of tellurium-containing imidodiphosphinate ligands: preparation of two morphologies of phase-pure PbTe from a single-source precursor.

机构信息

Department of Chemistry, University of Calgary, Calgary, AB T2N 1N4, Canada.

出版信息

Inorg Chem. 2010 Feb 1;49(3):1198-205. doi: 10.1021/ic9021728.

DOI:10.1021/ic9021728
PMID:20041664
Abstract

Group 14 metal complexes of heavy chalcogen-centered anions, M(TeP(i)Pr(2))(2)N (5, M = Sn; 6, M = Pb) and M(TeP(i)Pr(2)NP(i)Pr(2)Se)(2) (7, M = Sn; 8, M = Pb), were synthesized in 64-89% yields by metathesis of alkali-metal salts of the ligands with group 14 metal dihalides. Crystallographic characterization of the complexes revealed that 5, 6, and 8 engage in metal...chalcogen secondary bonds to generate dimers, whereas 7 is monomeric in the solid state. Multinuclear ((1)H, (31)P, (77)Se, and (125)Te) solution NMR data for these homoleptic complexes evinced dynamic behavior leading to the equivalence of the two ligand environments. The Pb(II) complex 6 was utilized as a single-source precursor to micrometer-scale lead telluride particles via two divergent techniques: aerosol-assisted chemical vapor deposition of the complex in THF/CH(2)Cl(2) solution onto glass substrates yielded rectangular prisms, while solution injection of 6 in tri-n-octylphosphine onto Si/SiO(2)(100) substrates heated to 200-220 degrees C resulted in the formation of wires. PXRD and EDX analysis of the products confirmed the phase purity of the PbTe materials.

摘要

14 族金属配合物的重硫属阴离子,M(TeP(i)Pr(2))(2)N(5,M=Sn;6,M=Pb)和 M(TeP(i)Pr(2)NP(i)Pr(2)Se)(2)(7,M=Sn;8,M=Pb),通过碱金属盐与 14 族金属二卤化物的复分解反应以 64-89%的产率合成。配合物的晶体结构表征表明,5、6 和 8 与金属发生次级硫属键相互作用,生成二聚体,而 7 在固态中为单体。这些均配体配合物的多核((1)H、(31)P、(77)Se 和 (125)Te)溶液 NMR 数据显示存在动态行为,导致两个配体环境的等价性。Pb(II)配合物 6 被用作微米级碲化铅颗粒的单源前体,通过两种发散技术:在玻璃基板上的 THF/CH(2)Cl(2)溶液中用气溶胶辅助化学气相沉积该配合物,得到矩形棱柱;而在 200-220°C 加热的 Si/SiO(2)(100)基板上,将 6 溶液注入三正辛基膦中,则形成了线材。产物的 PXRD 和 EDX 分析证实了 PbTe 材料的相纯度。

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