Preparation of 1, 3‐Diphenylselenophenotetraazaporphyrinato Ruthenium(II) Bis(4‐methylpyridine) by the Reaction of 3, 4‐Dicyano‐2, 5‐diphenylselenophene and Phthalonitrile: Its Optical and Electrochemical Properties. Issue 5 (23rd May 2014)

• Record Type: Journal Article
• Authors: Kimura, Takeshi; Murakami, Naoko
• Is Part Of: Heteroatom chemistry. Volume 25:Issue 5(2014:Sep.)
• Page Start: 428
• Page End: 433
• Publication Date: 2014-05-23
• Subjects: Heterocyclic chemistry -- Periodicals; 547.59
• DOI: 10.1002/hc.21178
• Languages: English
• ISSNs: 1042-7163

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>2, 5‐Diphenylselenophene (<bold>2a</bold>) was treated with bromine and then copper(I) cyanide to produce 3, 4‐dicyano‐2, 5‐diphenylselenophene (<bold>4</bold>). Compound <bold>4</bold> was mixed with phthalonitrile, and the mixture was reacted with ruthenium(III) trichloride and 4‐methylpyridine in the presence of 1, 8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in refluxed 2‐ethoxyethanol to give 1, 3‐diphenylselenophenotetraazaporphyrinato ruthenium(II) bis(4‐methylpyridine) (<bold>6</bold>). The structure of <bold>6</bold> was determined by ¹H NMR and fast atom bombardment mass spectrometry (FABMS). In the ¹H NMR spectrum, the signals of 4‐methylpyridine coordinating to the central ruthenium atom were observed at a higher magnetic field than those of free 4‐methylpyridine itself but at a lower magnetic field than those of phthaocyaninato ruthenium(II) bis(4‐methylpyridine) (<bold>7</bold>). The ⁷⁷Se NMR spectrum of <bold>6</bold> showed one singlet peak at δ = 759.5 ppm, which is a lower magnetic field than those of <bold>2a</bold> and <bold>4</bold>. The Q band absorption of <bold>6</bold> (λ_max = 660 nm) lies at a longer wavelength than does that of <bold>7</bold>. Oxidation and reduction potentials of <bold>6</bold> were measured with cyclic voltammetry using Ag/AgNO₃ as a reference electrode.</p> </abstract>