Electronic structure of mononuclear bis(1,2-diaryl-1,2-ethylenedithiolato)iron complexes containing a fifth cyanide or phosphite ligand: a combined experimental and computational study

A series of mononuclear square-based pyramidal complexes of iron containing two 1,2-diaryl-ethylene-1,2-dithiolate ligands in various oxidation levels has been synthesized. The reaction of the dinuclear species Fe(III)2(1L*)2(1L)2]0, where (1L)2- is the closed shell di-(4-tert-butylphenyl)-1,2-ethylenedithiolate dianion and (1L*)1- is its one-electron-oxidized pi-radical monoanion, with N(n-Bu)4]CN in toluene yields dark green crystals of mononuclear N(n-Bu)4]Fe(II)(1L*)2(CN)] (1). The oxidation of 1 with ferrocenium hexafluorophosphate yields blue Fe(III)(1L*)2(CN)] (1ox), and analogously, a reduction with Cp2Co] yields Cp2Co]N(n-Bu)4]Fe(II)(1L*)(1L)(CN)] (1red); oxidation of the neutral dimer with iodine gives Fe(III)(1L*)2I] (2). The dimer reacts with the phosphite P(OCH3)3 to yield Fe(II)(1L*)2{P(OCH3)3}] (3), and Fe(III)2(3L*)2(3L)2] reacts with P(OC6H5)3 to give Fe(II)(3L*)2{P(OC6H5)3}] (4), where (3L)2- represents 1,2-diphenyl-1,2-ethylenedithiolate(2-). Both 3 and 4 were electrochemically one-electron oxidized to the monocations 3ox and 4ox and reduced to the monoanions 3red and 4red. The structures of 1 and 4 have been determined by X-ray crystallography. All compounds have been studied by magnetic susceptibility measurements, X-band EPR, UV-vis, IR, and M?ssbauer spectroscopies. The following five-coordinate chromophores have been identified: (a) Fe(III)(L*)2X]n, X = CN-, I- (n = 0) (1ox, 2); X = P(OR)3 (n = 1+) )3ox, 4ox) with St = 1/2, SFe = 3/2; (b) Fe(II)(L*)2X]n, X = CN-, (n = 1-) (1); X = P(OR)3 (n = 0) (3, 4) with St = SFe = 0; (c) Fe(II)(L*)(L)X]n <--> Fe(II)(L)(L*)X]n, X = CN- (n = 2-) (1red); X = P(OR)3 (n = 1-) (3red, 4red) with St = 1/2, SFe = 0 (or 1). Complex 1ox displays spin crossover behavior: St = 1/2 <--> St = 3/2 with intrinsic spin-state change SFe = 3/2 <--> SFe = 5/2. The electronic structures of 1 and 1(ox) have been established by density functional theoretical calculations: Fe(II)(1L*)2(CN)]1- (SFe = 0, St = 0) and Fe(III)(1L*)2(CN)]0 (SFe = 3/2, St = 1/2).