Electrocatalytic oxidation and detection of hydrazine at gold electrode modified with iron phthalocyanine complex linked to mercaptopyridine self-assembled monolayer

Electrocatalytic oxidation and detection of hydrazine in pH 7.0 conditions were studied by using gold electrode modified with self-assembled monolayer (SAM) films of iron phthalocyanine (FePc) complex axially ligated to a preformed 4-mercaptopyridine SAMs. The anodic oxidation of hydrazine in neutral pH conditions with FePc-linked-mercaptopyridine-SAM-modified gold electrode occurred at low overpotential (0.35 V versus Ag|AgCl) and the treatment of the voltammetric data showed that it was a pure diffusion-controlled reaction with the involvement of one electron in the rate-determining step. The mechanism for the interaction of hydrazine with the FePc-SAM is proposed to involve the Fe^(III)Pc/Fe^(II)Pc redox process. Using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), hydrazine was detected over a linear concentration range of 1.3 × 10⁻⁵ to 9.2 × 10⁻⁵ mol/L with low limits of detection (ca. 5 and 11 μM for OSWV and CV, respectively). At concentrations higher than 1.2 × 10⁻⁴ mol/L the anodic peak potential shifted to 0.40 V (versus Ag|AgCl), and this was interpreted to be due to kinetic limitations resulting from the saturation of hydrazine and its oxidation products onto the redox-active monolayer film. This type of metallophthalocyanine-SAM-based electrode is a highly promising electrochemical sensor given its ease of fabrication, good catalytic activity, stability, sensitivity and simplicity.     

Metal deposition onto thiol-covered gold: Platinum on a 4-mercaptopyridine SAM

In this study we describe details of a new technique that allows to deposit metal on top of a self-assembled monolayer (SAM). Monoatomic high platinum islands were formed on a 4-mercaptopyridine SAM on Au(1 1 1) by first immersing the SAM-covered gold electrode in an aqueous solution of K₂PtCl₄ without potential control to allow Pt(II) ions to form a complex with the pyridine nitrogen. The complexed Pt(II) ions were then reduced electrochemically to Pt(0) after transferring the electrode to a Pt(II) ion-free solution. Upon reduction, monoatomic high Pt islands were observed in STM, the total coverage depending on the time for complexation. Ex situ angle-resolved XPS studies reveal that the Pt islands indeed reside on top of the SAM.     

Synthesis of homo- and heteronuclear ruthenium-gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] and [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)]

The reaction between [Ru₃(CO)₁₀(NCMe)₂] and [AuClPPh₃] gave compound [Ru₃(CO)₁₀(μ-Cl)(μ-AuPPh₃)] (1) in quantitative yield under very mild conditions. The reaction of 1 with 4-mercaptopyridine (4-pyS) using ultrasonic reaction conditions gave the heteronuclear compound [Ru₃(CO)₁₀(μ-AuPPh₃)(μ-SC₅H₄N)] (2) in moderate yield. There was no spectroscopic evidence that indicates the formation of the hydride isolobal analog in this reaction. The homonuclear cluster [Ru₃(CO)₈(μ-H)(μ-SC₅H₄N)(μ-dppe)] (3) was prepared by a selective reaction employing the ruthenium-diphosphine derivative [Ru₃(CO)₁₀(μ-dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) with 4-pyS in THF solution. The isolobal analog to compound 3, compound [Ru₃(CO)₈(μ-AuPPh₃)(μ-SC₅H₄N)(μ-dppe)] (4) was synthesized by the reaction between compound 2 and dppe in refluxing dichloromethane. Compounds 1-4 were characterized in solution by spectroscopic methods and the molecular structure of compounds 2 and 3 in the solid state was obtained by single crystal X-ray diffraction studies.     

银电极上2-巯基吡啶和4-巯基吡啶自组装单层的原位表面增强拉曼光谱电化学

利用原位表面增强拉曼散射(SERS)技术,分别观察了2-巯基吡啶和4-巯基吡啶在银表面自组装单层的电化学行为。实验结果表明,随着电位的负移,2-巯基吡啶和4-巯基吡啶分子在银表面均呈现出先倾斜再垂直然后倾斜的吸附取向改变过程。但发生完全脱附的电位则有所不同。     

Reactivity of [Os3(CO)10(NCMe)2] and [Os3(CO)10(μ-Cl)(μ-AuPPh3)] with 4-mercaptopyridine: X-ray structure of [Os3(CO)10(μ-H)(μ-SC5H4N)] and [Os3(CO)10(μ-AuPPh3)(μ-SC5H4N)]

The compound [Os₃(CO)₁₀(μ-Cl)(μ-AuPPh₃)] (2) was prepared from the reaction between [Os₃(CO)₁₀(NCMe)₂] (1) and [AuClPPh₃] under mild conditions. The reaction of 2 with 4-mercaptopyridine (4-pyS) ligand yielded compounds [Os₃(CO)₁₀(μ-H)(μ-SC₅H₄N)] (4), formed by isolobal replacement of the fragment [AuPPh₃]⁺ by H⁺ and [Os₃(CO)₁₀(μ-AuPPh₃)(μ-SC₅H₄N)] (5). [Os₃(CO)₁₀(μ-H)(μ-SC₅H₄N)] (4) was also obtained by substitution of two acetonitrile ligands in the activated cluster 1 by 4-pyS, at room temperature in dichloromethane. Compounds 2-5 were characterized spectroscopically and the molecular structures of 4 and 5 in the solid state were obtained by single crystal X-ray diffraction studies.