Generation of substrate-binding sites by electrochemical reduction of cis-[Fe2(cp)2(μ-SMe)2(MeCN)(L)]2+ (L = CO or MeCN). Reactivity of the sites toward CO and tBuNC. Crystal structure of [Fe2(cp)2(μ-SMe)2(CO)(MeCN)][BF4]2·CH2Cl2

Synthesis, characterization, and structural study of iron–sulfur core {Cp2Fe2(μ-SEt)2} complexes

“…The Fe-Fe distances of 1, 2, 3 and 4 of 2.638(2), 2.6315(9), 2.6372(10) and 2.6467(8) Å, respectively, agree well with comparable values for [Cp 2 Fe 2 (lSEt) 2 (NCMe) 2 ] 2+ and other related complexes [10,17]; they fall in the 2.5-2.8 Å range which are characteristic of two-electron Fe-Fe bond [10,17]. (12) 15.5341 (7) 24.0327 (6) 11.6578 (5) 16.0882 (2) 13.0397 (5) 14.9075(9) b (Å) 10.0827 (10) 15.3085 (7) 10.3123 (2) 15.5137 (6) 16.3991 (2) 17.9504 (8) 15.9513(10) c (Å) 10.9801 (12) 28.3557 (13) 19.0380 (6) 16.9204 (7) 18.6519 (2) 19.5170 (11) The substitutionally labile acetonitrile ligands in complex 1 are readily replaced by diphosphine ligands (Scheme 2). Thus, the synthesis of complex [Cp 2 Fe 2 (l-SEt) 2 (l-dppm)](PF 6 ) 2 (5) become accessible by reaction of complex 1 and dppm.…”

“…Similar structural features are observed for the related thiolate-bridged CpFe complexes 1 and 2 that have been reported [17], but we could not find out their detail crystallography data in CSD database. The Fe-S distances in the range 2.17-2.26 Å are comparable to those of other thiolate-bridged diiron centers with Fe(III) centers [10,17]. The Fe-Fe distances of 1, 2, 3 and 4 of 2.638(2), 2.6315(9), 2.6372(10) and 2.6467(8) Å, respectively, agree well with comparable values for [Cp 2 Fe 2 (lSEt) 2 (NCMe) 2 ] 2+ and other related complexes [10,17]; they fall in the 2.5-2.8 Å range which are characteristic of two-electron Fe-Fe bond [10,17].…”

“…Similar electrochemical study results are also observed for the related thiolate-bridged CpFe complexes [10,17]. By using the E 1/2 values for the two redox couples, a comproportionation constant, K com , for the iron-sulfur core {Cp 2 Fe 2 (l-SEt) 2 } complexes were calculated according to the equilibrium in Eq.…”

“…Among synthetic iron-sulfur complexes, dinuclear cyclopentadienyl thiolate-bridged species are a well-established class of compounds [2,9]. A series of studies on the iron-sulfur core {Cp 2 Fe 2 (l-SR) 2 } complexes (R = alkyl or aryl), of their redox and/or their crystal structures have reported [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. However, their reactivity has been comparatively little explored [10,16,17].…”

Activation of proton by the two-electron reduction of a di-iron organometallic complex

“…The acid concentration in the electrolyte was varied by addition of a measured volume of 0.2 M HOTs or 0.2 M HOAc in CH 3 CN. The bi-electronic reduction of complex 1 was confirmed by using cis-Fe 2 (SMe) 2 -(CO) 2 Cp 2 [19] as an internal voltammetric standard, with the reasonable assumption that these two binuclear iron complexes have a very similar diffusion coefficient. Simulations were performed with the Electrochemical Simulation Package (ESP v.2.4) by Carlo Nervi.…”