Fluorine Substitution of TCNQ Alters the Redox-Driven Catalytic Pathway for the Ferricyanide-Thiosulfate Reaction.

Mechanistic variation in catalysis through substituent-based redox tuning is well established. Fluorination of TCNQ (TCNQ=tetracyanoquinodimethane) provides ~850 mV variation in the redox potentials of the TCNQF n 0 / 1 - ${{{\rm {TCNQF}}}_{{\rm {n}}}^{{\rm {0/1-}}}}$ and TCNQF n 1 - / 2 - ${{{\rm {TCNQF}}}_{{\rm {n}}}^{{\rm {1-/2-}}}}$ (n=0, 2, 4) processes. With TCNQF 4 1 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {1-}}}}$ , catalysis of the kinetically very slow ferrocyanide-thiosulfate redox reaction in aqueous solution occurs via a mechanism in which the catalyst TCNQF 4 1 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {1-}}}}$ is reduced to TCNQF 4 2 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {2-}}}}$ when reacting with S 2 O 3 2 - ${{{\rm {S}}}_{{\rm {2}}}{{\rm {O}}}_{{\rm {3}}}^{{\rm {2-}}}}$ which is oxidised to S 4 O 6 2 - ${{{\rm {S}}}_{{\rm {4}}}{{\rm {O}}}_{{\rm {6}}}^{{\rm {2-}}}}$ . Subsequently, TCNQF 4 2 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {2-}}}}$ reacts with [ Fe ( CN ) 6 ]​ 3 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {3-}}}}$ to form [ Fe ( CN ) 6 ]​ 4 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {4-}}}}$ and reform the TCNQF 4 1 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {1-}}}}$ catalyst, in another thermodynamically favoured process. An analogous mechanism applies with TCNQF 2 1 - ${{{\rm {TCNQF}}}_{{\rm {2}}}^{{\rm {1-}}}}$ as a catalyst. In contrast, since the reaction of S 2 O 3 2 - ${{{\rm {S}}}_{{\rm {2}}}{{\rm {O}}}_{{\rm {3}}}^{{\rm {2-}}}}$ with TCNQ 1 - ${{{\rm {TCNQ}}}^{{\rm {1-}}}}$ is thermodynamically unfavourable, an alternative mechanism is required to explain the catalytic activity observed in this non-fluorinated system. Here, upon addition of TCNQ 1 - ${{{\rm {TCNQ}}}^{{\rm {1-}}}}$ , reduction of [ Fe ( CN ) 6 ]​ 3 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {3-}}}}$ to [ Fe ( CN ) 6 ]​ 4 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {4-}}}}$ occurs with concomitant oxidation of TCNQ 1 - ${{{\rm {TCNQ}}}^{{\rm {1-}}}}$ to TCNQ 0 ${{{\rm {TCNQ}}}^{{\rm {0}}}}$ , which then acts as the catalyst for S 2 O 3 2 - ${{{\rm {S}}}_{{\rm {2}}}{{\rm {O}}}_{{\rm {3}}}^{{\rm {2-}}}}$ oxidation. Thermodynamic data explain the observed differences in the catalytic mechanisms. CuTCNQF n ${{{\rm {CuTCNQF}}}_{{\rm {n}}}}$ (n=0, 4) also act as catalysts for the ferricyanide-thiosulfate reaction in aqueous solution. The present study shows that homogeneous pathways are available following addition of these dissolved materials. Previously, these CuTCNQF n ${{{\rm {CuTCNQF}}}_{{\rm {n}}}}$ (n=0, 4) coordination polymers have been regarded as insoluble in water and proposed as heterogeneous catalysts for the ferricyanide-thiosulfate reaction. Details and mechanistic differences were established using UV-visible spectrophotometry and cyclic voltammetry.

Revisiting the TCNQF4 0/1-/2- Catalysis Mechanism for the [Fe(CN)6 ]3-/4- -S2 O3 2- /S4 O6 2- Redox Reaction.

Published data suggest that sparingly soluble metal complexes of TCNQF n 1 - ${{\rm{TCNQF}}_{\rm{n}}^{{\rm{1 - }}} }$ , where n=0, 1, 2, 4, can act as heterogeneous catalysts for the kinetically very slow [ Fe ( CN ) 6 ]​ 3 - / 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - /4 - }}} }$ - S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ / S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ reaction in aqueous solution. This study shows that the coordination polymer CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ , participates as a homogeneous catalyst via an extremely small concentration of dissolved TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ . This finding suggests that the generally accepted mechanism of catalysis by TCNQF 4 ${{\rm{TCNQF}}_{\rm{4}} }$ based solids needs to be revisited to ascertain the role of homogeneous pathways. In the present study, UV-visible spectrophotometry was used to examine the catalysis of the aqueous redox reaction of [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ (1.0 mM) with S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ (100 mM) in the presence of (i) a precursor catalyst, TCNQF 4 0 ${{\rm{TCNQF}}_{\rm{4}}^{\rm{0}} }$ ; (ii) the catalyst, TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ , as the water soluble Li+ salt; and (iii) CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ . A homogeneous reaction scheme that utilises the TCNQF 4 1 - / 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - /2 - }}} }$ couple is provided. In the case of TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ derived from highly soluble LiTCNQF 4 ${{\rm{LiTCNQF}}_{\rm{4}} }$ , quantitative conversion of 1.0 mM S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ to 0.50 mM S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ occurs with complete reduction of [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ to [ Fe ( CN ) 6 ]​ 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{4 - }}} }$ being rapidly accelerated by sub-micomolar concentrations of TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ . TCNQF 4 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{2 - }}} }$ generated in the catalytic cycle, reacts with [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ to reform TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ and produce [ Fe ( CN ) 6 ]​ 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{4 - }}} }$ . Along with the rapid catalytic reaction, the sluggish competing reaction between TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ and S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ occurs to give TCNQF 4 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{2 - }}} }$ , which is protonated to HTCNQF 4 1 - ${{\rm{\;HTCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ , along with a trace amount of S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ . On addition of the precursor catalyst, TCNQF 4 0 ${{\rm{TCNQF}}_{\rm{4}}^{\rm{0}} }$ , rapid reduction with S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ occurs to form TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ - the active catalyst. CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ added to water is shown to be sufficiently soluble to provide adequate TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ to act as the catalyst for the [ Fe ( CN ) 6 ]​ 3 - / 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - /4 - }}} }$ - S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ / S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ reaction.

Revisiting the TCNQF 4 0 / 1 - / 2 - ${{\bf TCNQF}_{\bf 4}

The front cover artwork was done by Michelle Farrelly, a member of the Martin group at Monash University. The image represents a perspective of a cuvette in which the catalysis of the thiosulfate-ferricyanide reaction was achieved by a TCNQF4 -based redox reaction in aqueous solution. The primary method used to monitor these reactions was spectrophotometry. Read the full text of the Research Article at 10.1002/cphc.202200942.