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首页> 外文期刊>New Journal of Chemistry >Reactivity of hemi-labile pyridyl and pyrimidyl derived chalcogen ligands towards group 10 metal phosphine precursors
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Reactivity of hemi-labile pyridyl and pyrimidyl derived chalcogen ligands towards group 10 metal phosphine precursors

机译：半不稳定吡啶基和嘧啶衍生的硫氨基配体朝向10金属膦前体的反应性

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摘要

A drive to understand the reactivity of hemi-labile organoselenide and telluride ligand systems has made this area of research increasingly popular. For this purpose, various metal systems have been applied. Among them, group 10 metal precursors have been exploited predominantly because the resulting complexes are important as catalytic, semiconductor and supercapacitor materials. The wide applicability of these compounds has driven us to explore the chemistry of N-heterocyclic-based ligand systems. Overall, this research deals with the reactivity of N-heterocyclic dichalcogenides Ar2E2 (Ar = C5H4N, C5H3(3-Me)N, C4H3N2, C4H(4,6-Me)N-2; E = Se, Te) and their sodium salts (generated by the reductive cleavage of E-E bonds through NaBH4) towards group 10 metal phosphine precursors via oxidative addition and substitution routes. The oxidative addition reactions of [M(P-P)(2)] (M = Pd, Pt) and substitution reactions of [MCl2(P-P)] (M = Ni, Pd, Pt) with diorgano dichalcogenide and sodium salts of N-heterocyclic selenolate ligands afforded exclusively mononuclear compounds [M(SeAr)(2)(P-P)] (M = Ni, Pd, Pt; Ar = C5H4N, C5H3(3-Me)N, C4H3N2, C4H(4,6-Me)N-2; P-P = dppe, dppp, dppf), however the pyrimidyl selenolate-derived mononuclear compounds transformed to trinuclear products after prolonged standing in chlorinated solvents. In contrast to the selenium analogues, all probable mono to tri nuclear complexes of tellurium were isolated depending upon the metal and phosphine, and the nature of the solvent. The isolation of various products depended on the comparable bond dissociation energies of the Te-Te and Te-C bonds. Among these, a ferrrocenyl auxiliary phosphine ligand-based mononuclear tellurolate compound [Pd(TeC5H4N)(2)(dppf)] was used for H2S gas sensor applications. The efficiency of a thin film of this compound was 75% with a sensitivity of down to 5 ppm at room temperature.
机译：一种了解Hemi-Libile有机硒烯和碲化物配体系统的反应性使得该研究领域越来越受欢迎。为此目的，已应用各种金属系统。其中，第10组金属前体主要被利用，因为所得复合物是催化，半导体和超级涂物材料的重要性。这些化合物的广泛适用性已经驱动我们探讨基于N-杂环基配体系的化学。总体而言，该研究涉及N-杂环二甲基甲基化物AR2E2的反应性（Ar = C5H4N，C5H3（3-ME）N，C4H3N2，C4H（4,6-ME）N-2; E = SE，TE）及其钠通过氧化添加和替代途径（通过NaBH4通过NaBH 4的还原切割）盐（通过NaBH4的还原粘合产生）。 [M（pp）（2）]（m = pd，pt）和用二氧化硫甲基化物和n-杂环的钠盐的[Mcl 2（pp）]（m = Ni，Pd，Pt）取代的氧化添加反应和取代反应硒固盐配体，完全单核化合物[m（σ）（2）（pp）]（m = Ni，Pd，Pt; Ar = C5H4N，C 5 H 3（3-Me）N，C4H3N2，C4h（4,6-ME）n -2; pp = DPPE，DPPP，DPPF），但是在长时间站立在氯化溶剂后，嘧啶硒醇衍生的单核化合物转化为干细胞的单核化合物。与硒类似物相比，根据金属和膦和溶剂的性质，分离所有可能的单核复合物的所有可能的单核复合物，以及溶剂的性质。各种产品的分离依赖于TE-TE和TE-C键的可比粘接性脱离能量。其中，用于H2S气体传感器应用，使用基于二氧化苯基助剂的单核蛋白化合物[Pd（TEC5H4N）（2）（2）（DPPF）]。该化合物的薄膜的效率为75％，在室温下敏感性降至5ppm。

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