Versatile Reactivity of CH3CN‐Coordinated Nickel‐Iron Heterodimetallic Complexes with Cp* Ligand on Diazadithiolate (N2S2) or Dithiadithiolate (S4) Platforms. Issue 18 (28th May 2015)

• Record Type: Journal Article
• Authors: Yang, Dawei; Li, Yang; Su, Linan; Wang, Baomin; Qu, Jingping
• Is Part Of: European journal of inorganic chemistry. Issue 18(2015)
• Page Start: 2965
• Page End: 2973
• Publication Date: 2015-05-28
• Subjects: Nickel -- Iron -- S ligands -- ­Bioinorganic chemistry -- Enzyme models -- Electrocatalysis; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500304
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: By using 3, 7‐dithianonane‐1, 9‐dithiol (S4 ) and N, N′ ‐dimethyl‐ N, N′ ‐bis(2‐mercaptoethyl)ethylenediamine (N2 S2 ) as ligands, two CH3 CN‐coordinated nickel‐iron heterodimetallic complexes, [NiS4 Fe(CH3 CN)Cp*][PF6 ] (1a ) and [NiN2 S2 Fe(CH3 CN)Cp*][PF6 ] (1b ) (Cp* = η 5 ‐C5 Me5 ), were synthesized and characterized spectroscopically and crystallographically. Reactivities of1a and1b towards CO, CH2 Cl2, HBF4, and NOPF6 have also been investigated. A series of complexes coordinated with small molecules [NiS4 Fe(L)Cp*][PF6 ] n [ n = 1, L = Cl (2a ), CO (3a ); n = 2, L = NO (4a )], [NiN2 S2 Fe(L)Cp*][PF6 ] [L = Cl (2b ), CO (3b )] were obtained. We also studied the redox properties of2a, 2b, 3a, and3b by cyclic voltammetry in CH2 Cl2 and in CH3 CN solution. Complex3a was found to be an excellent electrocatalyst for proton reduction from HBF4 . Abstract : CH3 CN‐coordinated nickel‐iron heterodimetallic complexes [NiS4 Fe(CH3 CN)Cp*][PF6 ] and [NiN2 S2 Fe(CH3 CN)Cp*][PF6 ], and complexes with small molecules coordinated [NiS4 Fe(L)Cp*][PF6 ] n ( n = 1, L = Cl, CO; n = 2, L = NO) and [NiN2 S2 Fe(L)Cp*][PF6 ] (L = Cl, CO) were synthesized and characterized crystallographically. One of the complexes is an excellent electrocatalyst for proton reduction.