Synthesis, Structure and Physical Properties of Tetrabutylammonium Salts of Nickel Complexes with the New Ligand dcbdt = 4,5-dicyanobenzene-1,2-dithiolate, [Ni(dcbdt)2]z− (z = 0.4, 1, 2)

Abstract

The synthesis and characterization of the new aromatic ortho-dithiol, 4,5-dicyanobenzene-1,2-dithiol (3) is reported. This compound was used to prepare tetrabutylammonium salts of novel nickel complexes; the nickel(II) salt (nBu 4 N) 2 -[Ni(dcbdt) 2 ] (4), the nickel(III) salt (nBu 4 N) 2 [Ni(dcbdt) 2 ] 2 (5), and the partially oxidized Ni III/IV salt (nBu 4 N) 2 [Ni(dcbdt) 2 ] 5 (6). (dcbdt = 4,5-dicyanobenzene-1,2-dithiolate). The Ni II complex presents a square-planar coordination geometry and is diamagnetic, while in the paramagnetic Ni III complex

Ligand‐Based PCET Reduction in a Heteroleptic Ni(bpy)(dithiolene) Electrocatalyst Giving Rise to Higher Metal Basicity Required for Hydrogen Evolution

“…All solvents and reagents were of the highest qualities available and were used as received without further purification. 4,5‐Dicyanobenzene‐1,2‐dithiol (dcbdtH 2 ), ( n ‐Bu 4 N) 2 [Ni II (dcbdt) 2 ], and Ni II (bpy)(qdt) (qdt=quinoxaline‐2,3‐dithiolate) were synthesized as previously described.…”

Organometallic dithiolene complexes of benzenedithiolate analogues with π-coordinating and π-interacting Cp* ligand

“…Cp*H (1,2,3,4,5-pentamethylcyclopentadiene), 4,5-dichlorophthalonitrile, and 5,6-dichloropyrazine-2,3-dicarbonitrile were obtained from Wako Pure Chemicals Industries, Ltd. RhCl 3 Á3H 2 O and IrCl 3 ÁnH 2 O were obtained from STREM Chemicals. [Cp*Co(-CO) 2 ] [41], [Cp*Co(CO)I 2 ] [42], [Cp*M(Cl)(l-Cl)] 2 (M = Rh, Ir) [29], (PhCH 2 ) 2 (dcbdt) (1) [24], and (PhCH 2 ) 2 (dcdmp) (2) [43] were prepared by literature methods. Mass and IR spectra were recorded on a JEOL JMS-D300 and a Shimadzu Model FTIR 8600PC instruments, respectively.…”

“…However, there is a synthetic difficulty using the precursor [Cp* 2 Ni]. Almeida et al have reported a rich family of square-planar or tetrahedral bisdithiolene complexes (M = Fe, Co, Ni, Pd, Pt, Cu, Au and Zn) based on the dcbdt [23,24] and the dcdmp ligands [25,26] and their structural, magnetic and electrical conductive properties have been studied as well [23][24][25][26]. Furthermore, Ueda et al have reported the oxo-vanadium bisdithiolene complex of the dcbdt, [O@V(dcbdt) 2 ] [27].…”

“…Here we report on the synthetic procedure of [Cp*M(dcbdt)] (or dcdmp), their spectral, electrochemical characterizations, and crystal structure determinations, considering plane-to-plane interactions as well. Almeida et al have already reported the preparation of dithiolene precursor, which has been the dcbdt 2À ligand protected by two benzyl groups (PhCH 2 ) 2 (dcbdt) (1), and then 1 has treated with a strong base to isolate H 2 dcbdt [24]. Furthermore, the H 2 dcbdt has reacted with a metal source in the presence of a base again to give the corresponding M(dcbdt) complexes [23,24].…”

“…Almeida et al have already reported the preparation of dithiolene precursor, which has been the dcbdt 2À ligand protected by two benzyl groups (PhCH 2 ) 2 (dcbdt) (1), and then 1 has treated with a strong base to isolate H 2 dcbdt [24]. Furthermore, the H 2 dcbdt has reacted with a metal source in the presence of a base again to give the corresponding M(dcbdt) complexes [23,24]. For preparations of some dcdmp complexes, they have used a direct generation of the dcdmp 2À from 5,6-dichloropyrazine-2,3-dicarbonitrile and sodium sulfide [26].…”