2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1-bis(diethylamino)ethylium bis(perchlorate)

Abstract

The title salt, C20H42N4S2 2+·2ClO4 −, was obtained from the reaction of bis­(diethyl­amino)­carbeniumdithio­carboxyl­ate, (Et2N)2C2S2, with Fe(ClO4)2·6H2O in CH2Cl2. The title compound, in which one of the S atoms of (Et2N)2C2S2 is bound to a 1,1-bis­(diethyl­amino)­ethane moiety, has two carbenium C atoms, and the charge compensation is provided by two perchlorate anions. The N2C—CS2 bond length is 1.512 (4) Å, corresponding to a C—C single bond, and the dihedral angle between N2C– and –CS2 planes [72.0 (2)°] is smaller than that of (Et2N)2C2S2 [82.0 (1)°]. The crystal structure features C—H⋯S hydrogen bonds.

Observation of the First Spin Crossover in an Iron(II) Complex with an S6 Coordination Environment: Tris[bis(N,N‐diethylamino)carbeniumdithiocarboxylato]iron(II) Hexafluorophosphate

“…The originalg reen solutiong radually turned brown,a nd brown crystals grew upon the addition of hexane. An X-ray crystallographic study of someofthe crystalsrevealed that two of the three EtLs were oxidized to give ad ithioperoxicarboxylate (EtLO), which formed ac ationic iron(II) complex [Fe II (EtL)(EtLO-O,S) 2 ](PF 6 ) 2 (2)i np lace of 1 ( Figure S4, Ta bles S6 [18] Synthesis of the iron(III) complex in the d 5 electronic structure was unsuccessful. For example, stirring am ixture of iron sources (e.g.,F eCl 2 ,F eCl 3 ,F e(ClO 4 ) 3 )a nd EtL in solvents (e.g., CH 2 Cl 2 ,C H 3 CN) under an Ar or air atmosphere resulted in the generation of ac omplex material( solvated iron specieso ro xidized species).…”

“…An X‐ray crystallographic study of some of the crystals revealed that two of the three EtLs were oxidized to give a dithioperoxicarboxylate (EtLO), which formed a cationic iron(II) complex [Fe II (EtL)(EtLO‐ O,S ) 2 ](PF 6 ) 2 ( 2 ) in place of 1 (Figure S4, Tables S6 and S7 in the Supporting Information). In addition, the perchlorate analogue of 1 , [Fe II (EtL) 3 ](ClO 4 ) 2 , degraded in Et 2 O over several months at ambient temperature to give an oxidized EtL of unique dimeric structure …”

Syntheses and Properties of Dinuclear Group 6 Metal Complexes with the Zwitterionic Sulfur Donor Ligand Bis(N,N-diethylamino)carbeniumdithiocarboxylate

“…The two-electron-reduced species were actually isolated in the solid state, and the structures were determined by X-ray analysis . On the other hand, in the oxidation process, the RL dimerizes to give the disulfide intermediate, through which a one-sulfur-eliminated species was finally obtained …”