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The reaction of [Fe2(CO)6(𝜇-toluene-3, 4-benzenedithiolate)]
1 and bidentate diphosphine, 1, 1′-bis(diphenylphosphino)ferrocene (dppf) has been studied. New complexes obtained have been characterized by various spectroscopic techniques as bioinspired models of the iron hydrogenase active site. The crystal structure of [Fe2(CO)5(𝜅1-dppfO)(𝜇-toluene-3, 4-benzenedithiolate)]4 is reported. -
Abstract. The reaction of the tetranuclear iron complex [μ4-Sulfido-bis{(μ-2-furylmethanethiolato) bis[tricarbonyliron](Fe—Fe)}] 1 with PPh3 was explored. The reaction leads to the formation of the monosubstituted complex [Fe2.μ-2-furylmethanethiolate)2.(CO)5.(PPh3)] 2. X-ray crystal structure has been reported for complex 2. Complexes 1 and 2 were found to be active catalysts for proton reduction. Complexes 1 and 2 showed comparable catalytic activity for proton reduction to dihydrogen.
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Supramolecular coordination complex [(Re(CO)3)2(dhnq)(L2)] (3) containing two fac-Re(CO)3 cores, rigid dianionic dhnq (H2-dhnq = 6,11-dihydroxy-5,12-naphthacenedione) motif and semi-rigid ditopic nitrogen donor 1,2-bis(2-nonylbenzimidazol-1-ylmethyl)benzene (o-Nbenzbix = L2) was synthesized.Compounds o-Nbenzbix and 3 were characterized using various analytical and spectroscopic methods. The electrochemical properties of 3 were studied using cyclic voltammetric measurements. SCCs [(Re(CO)3)2(-dhnq)(L1)] (1) and [(Re(CO)3)2(dhaq)(L1)] (2) possessing p-xylene spacer 1,4-bis(2-nonylbenzimidazol-1-ylmethyl)benzene (L1) and 1,4-dihydroxy-9,10-anthraquinone (H2-dhaq) were also synthesized as reported previously. SCCs 1–3 were investigated via electrochemical methods. A plot of the Randles-Sevcik equation yielded a straight line for complex 3 thus, establishing that the redox processes were diffusion-controlled.
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Macrocyclic butterfly iron cluster complexes: electrochemical investigations
The article primarily highlights the electrocatalytic activity towards proton reduction of macrocyclic tetranuclear iron complexes [Fe2(l-S(CH2)nS-l)(CO)6]2 (n = 4, 1 and n = 6, 2) with both acetic acid and trifluoroacetic acid as proton sources. Further, the electrochemical results have been compared with theanalogous pentanedithiolate-bridged tetranuclear complex, [Fe2(l-S(CH2)5S-l)(CO)6]2 A. The turnover frequency (TOF, acetic acid) for complexes 1 and 2 was found to be 5.7 h-1 and 9.1 h-1, respectively. An ECEC catalytic cycle (acetic acid) has been proposed for the tetranuclear iron complexes based on theexperimental data and known literature
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Reaction of Fe3(CO)12 and 2-mercaptobenzimidazole leads to the formation of a triiron sulphurcluster [Fe3(C7H6N2)(μ3-S)2(CO)8] 1 and a diiron monothiolate-bridged complex [Fe2(μ-2-mercaptobenzimidazole)2(CO)6] 2. The structures of the complexes were confirmed by various spectroscopic techniques(NMR, FTIR, UV-Vis), elemental analysis and mass spectrometry. FTIR spectra of 1 and 2 (in CH2Cl2)displayed peaks at 2069, 2022, 2006, 1965 and 2070, 2002, 1963 cm-1, respectively indicating the presenceof terminal carbonyls in the two complexes. Based on cyclic voltammetric measurements, complexes 1 and 2were found to catalyze the reduction of trifluoroacetic acid to produce dihydrogen (in CH3CN) at -1.68 Vand -1.58 V vs. Fc/Fc+, respectively.
The reaction of Fe3(CO)12 with 2-mercaptobenzimidazole led to the formation of an unusual triiron carbene cluster as the major product and a diiron monothiolate complex as the minor product. The di- and triiron clusters displayed electrocatalytic activity in acetonitrile in the presence of either acetic acid or trifluoroacetic acid as proton sources.
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Journal of Chemical Sciences
Volume 134, 2022
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