15634-63-6Relevant academic research and scientific papers
Preparation of dinuclear iron carbonyl compounds containing a three-electron CH2-S bridging fragment
Raubenheimer, Helgard G.,Linford, Lorna,Lombard, Anthonie Van A.
, p. 2062 - 2063 (1989)
Dithioacetals, CH2(SR1)(SR2), reacted with Fe(CO)5 under UV irradiation to give, after scission of an S-C bond, the butterfly complexes [Fe2(CO)6(μ-SR1)(μ-CH2SR 2
Iron(I)-Based Carbonyl Complexes with Bridging Thiolate Ligands as Light-Triggered CO Releasing Molecules (photoCORMs)
Suchland, Benedikt,Malassa, Astrid,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
, p. 125 - 132 (2020)
A series of thiolate ligands were used to synthesize diiron(I) hexacarbonyl bis(thiolates) for structural studies. Conversion of the corresponding thiols with triiron(0) dodecacarbonyl yields complexes of the type [{(CO)3Fe(μ-SR)}2]
A comparative study of the use of triethylammonium salts of the - anion in the synthesis of iron-gold clusters. Crystal structures of iPr)(μ-AuPPh3)> and
Delgado, Esther,Hernandez, Elisa,Rossell, Oriol,Seco, Miquel,Puebla, Enrique Gutierrez,Ruiz, Caridad
, p. 177 - 184 (1993)
Salts of the type (NEt3H) (R = iPr, tBu, Ph) react with in the presence of TlBF4 to produce the neutral iron-gold clusters (R = iPr, 1; R = tBu, 2; R = Ph, 3) in high yields.The structure of 1 has been determined by X-ray diffraction methods.Crystals are monoclinic, space group P21/c, with a = 11.373(1), b = 14.899(3), c = 17.997(8) Angstroem, β = 95.12(2) deg and Z = 4, R = 0.030 and R' = 0.0035 for 3579 unique reflections with I 2?(I).The basic skeleton consists of an Fe2Au triangle where the Fe-Fe bond is bridged by a carbonyl and a thiolate group.In contrast, the reaction of the salts (NEt3H)( (R = Et or C6F5) with does not afford the corresponding mixed iron-gold clusters, and the diiron mono- or di-substituted complexes (R = Et, 4; R = C6F5, 5) and (6) are obtained instead.The structure of 4 has been established by single-crystal X-ray diffraction studies.Crystals are triclinic, space group, P1, with a = 10.472(4), b = 11.329(2), c = 13.437(2) Angstroem, α = 80.34(2), β = 92.62(3), γ = 114.46(2) deg, and Z = 2, R = 0.027 and R' = 0.030 for 3732 unique reflections with I 2?(I).The Fe-Fe bond in 4 is almost symmetrically double-bridged by two thiolate ligands and the phosphine group attached to the Fe(1) is trans to the iron-iron bond.
Organosulphur-Transition-metal Chemistry. Part 6. Reactions of Cyclo-octatetraenyl and Cycloheptatrienyl Thioethers with Metal Carbonyls
Carleton, Susan C.,Kennedy, Fiona G.,Knox, Selby A. R.
, p. 2230 - 2234 (1981)
The compound C8H7SMe has been prepared by treating cyclo-octatetraenyl-lithium with MeSCl.Reaction with provides tricarbonyliron complexes and trans-; the former appears to undergo the characteristic oscillatory fluxional motion of such monosubstituted cyclo-octaterraene comlexes, but the latter is non-fluxional.Sulphur-C8H7 bond cleavage is also evident, in the formation of and , and of bicyclo-octatetraenyl when C8H7SMe and react.Similarly S-C7H7 bond cleavage is predominant in reactions of known C7H7SR-7 (R=Me or Ph) and new C7H7SBut-7 (from and Nat>) with a variety of metal carbonyls.Only is obtained with , and t)2(η-C5H5)2> with , but from complexes, t)(μ3-C7H7))> and 7-C7H7))> (R=Me or But) are isolated, containing the components of C7H7SR as separate ligands.Fluxional rotation of the C7H7 ring in the diruthenium comlexes is slowed at -100 deg C, shown by n.m.r. spectra which also restricted rotation about the S-But bond.
Reactions of complexes with thiazolyl-, oxazolyl- and imidazolyl-mercurials: a route to Fe2(CO)6 complexes containing an η1,η2-C=N bridge
Seyferth, Dietmar,Anderson, Lea L.,Davis, William M.
, p. 271 - 282 (1993)
The reaction of complexes of type with thiazolyl-, oxazolyl- and N-methylimidazolylmercurials gave products of type in moderate yield, as well as (μ-RS)2Fe2(CO)6 and elemental mercury.The crystal structure of 13b (Z=S, R=Et, R1=H) is described: space group P (No. 2), a=9.3478(6) Angstroem, b=11.4594(6) Angstroem, c=8.1005(4) Angstroem, α=97.511(5)o, β=108.221(5)o, γ=71.516(5)o, Z=2, R=0.060, RW=0.064 for 2552 observed reflections.
Syntheses, crystal structures, and electrochemical studies of dinuclear coordination compounds with the Fe2(CO)6 core
Shi, Yao-Cheng,Wu, Zhi-Dan,Hou, Xiao-Lei,Li, Zong-Wei,Wang, Yong
, p. 3603 - 3618 (2016)
Reaction of 2-C5H4?NCOSPh, generated from 2-C5H4NCO2H and PhSH in the presence of DCC, with Fe3(CO)12 affords (μ-κ2C,N-2-C5H4N)(μ-PhS)Fe2(CO)6 (1) and (μ-PhS)2Fe2(CO)6 (2). Reaction of (NC)2C=C(SMe)2, formed from NCCH2CN, CS2, and MeI in the presence of NaOH, with Fe3(CO)12 provides (μ-κ2C,S-(NC)2C=CSMe)(μ-MeS)Fe2(CO)6 (3) and (μ-MeS)2Fe2(CO)6 (4). All complexes have been fully characterized by EA, IR, 1H NMR, and 13C NMR spectroscopy and structurally determined by X-ray crystallography. In 1 and 3, the group attached to the bridging S is at the equatorial position. In 2, two phenyl groups are at equatorial positions. Two isomers of 4, ae-4?and ee-4,?can be separated by thin-layer chromatography. DFT calculations reveal that the Gibbs energy difference between ae-4 and ee-4 is ?2.17?kcal?mol?1 in THF and ?2.29?kcal?mol?1 in benzene, and the isomerization barrier between ae-4 and ee-4 is 14.92?kcal?mol?1 in THF and 16.84?kcal?mol?1 in benzene. All these results suggest that ae-4 is more stable than ee-4 in either THF or benzene, and the two isomers do not interconvert. Electrochemical studies of 1 and 3 demonstrate that using HOAc as a proton source 1 and 3 can catalyze H2 production.
Spectroscopic and electrochemical comparison of [FeFe]-hydrogenase active-site inspired compounds: Diiron monobenzenethiolate compounds containing electron-donating and withdrawing groups
Day, Ryan J.,Gross, Anthony J.,Donovan, Elizabeth S.,Fillo, Kyle D.,Nichol, Gary S.,Felton, Greg A.N.
, (2021)
The novel compounds [Fe2(μ-SC6H4-p-NO2)2(CO)6] (1), [Fe2(μ-SC6H4-p-tBu)(μ-SC6H4-p-NO2)(CO)6] (2), [Fe2(μ-SC6H4-p-tBu)2(CO)6] (3), [Fe2(μ-SC6H4-p-tBu)(μ-SC6H4-p-CF3)(CO)6] (4) and [Fe2(μ-SC6H4-p-OCH3)(μ-SC6H4-p-CF3)(CO)6] (5) have been characterized by 1H NMR, FTIR, elemental analysis, and cyclic voltammetry. X-ray crystallography of compounds 1 and 2 reveal an anti (ax,eq) S-aryl ligand orientation in the solid state. Carbonyl IR spectra and reduction potentials correlate strongly with Hammett constants of the electron donating/withdrawing groups. Evaluation for electrocatalytic formation of dihydrogen from acetic acid indicates a low overpotential of activity of 0.26 V for compound 5.
Synthesis and interconversions of reduced, alkali-metal supported iron-sulfur-carbonyl complexes
Shupp, J. Patrick,Rose, Amber R.,Rose, Michael J.
, p. 9163 - 9171 (2017/07/24)
We report the synthesis, interconversions and X-ray structures of a set of [mFe-nS]-type carbonyl clusters (where S = S2-, S22- or RS-; m = 2-3; n = 1-2). All of the clusters have been identified and characterized by single crystal X-ray diffraction, IR and 13C NMR. Reduction of the parent neutral dimer [μ2-(SPh)2Fe2(CO)6] (1) with KC8 affords an easily separable ～1-:-1 mixture of the anionic, dimeric thiolate dimer K[Fe2(SPh)(CO)6(μ-CO)] (2) and the dianionic, sulfido trimer [K(benzo-15-crown-5)2]2[Fe3(μ3-S)(CO)9] (3). Oxidation of 2 with diphenyl-disulfide (Ph2S2) cleanly returns the starting material 1. The Ph-S bond in 1 can be cleaved to form sulfide trimer 3. Oxidation of sulfido trimer 3 with [Fc](PF6) in the presence of S8 cleanly affords the all-inorganic persulfide dimer [μ2-(S)2Fe2(CO)6] (4), a thermodynamically stable product. The inverse reactions to form 3 (dianion) from 4 (neutral) were not successful, and other products were obtained. For example, reduction of 4 with KC8 afforded the mixed valence Fe(i)/Fe(ii) species [((FeI2S2)(CO)6)2FeII]2- (5), in which the two {Fe2S2(CO)6}2- units serve as bidendate ligands to a Fe(ii) center. Another isolated product (THF insoluble portion) was recrystallized in MeCN to afford [K(benzo-15-crown-5)2]2[((Fe2S)(CO)6)2(μ-S)2] (6), in which a persulfide dianion bridges two {2Fe-S} moieties (dimer of dimers). Finally, to close the interconversion loop, we converted the persulfide dimer 4 into the thiolate dimer 1 by reduction with KC8 followed by reaction with the diphenyl iodonium salt [Ph2I](PF6), in modest yield. These reactions underscore the thermodynamic stability of the dimers 1 and 4, as well as the synthetic and crystallization versatility of using the crown/K+ counterion system for obtaining structural information on highly reduced iron-sulfur-carbonyl clusters.
Unexpected fragmentation of phenyldithiobenzoate, formation and X-ray structure of [μ,η2(S,S)-1,2-(dithio)-1,2-(diphenylethylene)] diiron hexacarbonyl complex
Mousser, Hénia,Darchen, André,Mousser, Abdelhamid
, p. 786 - 791 (2010/06/16)
The reaction of Fe2(CO)9 with phenyldithiobenzoate PhCS2Ph 1 afforded four colored compounds: [(μ-η3(C,S,S)PhCS2Ph)]Fe2(CO) 6 2, (μ-S)2Fe3(CO)9 3, (μ-SPh)2Fe2(CO)6 4 and [μ-η2(S,S)][PhC(S){double bond, long}C(S)Ph]Fe2(CO)6 5. Complex 5 was characterized by X-ray crystallography. The formation of complexes 4 and 5 was unexpected since it involved a fragmentation of the organic ligand 1 during its reaction with Fe2(CO)9. The electrochemical studies of 1, complexes 2 and 3 were undertaken in order to get information about the chemical behaviors of the intermediates generated by electron transfer. The results of cyclic voltammetry studies of 2 and 1 suggested that the reaction of 1 with Fe2(CO)9 involved two competitive reactions: (i) a thermal reaction which led to the expected compounds 2 and 3 and (ii) an electron transfer reaction involving a fragmentation of starting ligand 1 led to the unexpected complex 5. The required electrons may be provided by iron during the thermal decay of complexes 2 or 3 or Fe2(CO)9.
Synthesis and spectroscopic characterisation of compounds with formula [{Fe2(SPh)2(CO)5}Ph2P(CH2)nPPh2{Fe(CO)4}] and [{Fe2(SPh)2(CO)5}2Ph2P(CH2)nPPh2] (n=3, 4 and 6)
Hourihane, Rosamund,Gray, Geraldine,Spalding, Trevor,Deeney, Tony
, p. 40 - 47 (2007/10/03)
This work describes the synthesis and characterisation of the title compounds. This is the second in a series of reactions involving iron bis-phosphine cluster compounds [{Fe3(CO)11}Ph2P(CH2)nPPh2{Fe(CO)4}] and [{Fe3(CO)11}2Ph2P(CH2)nPPh2] (n=3, 4 and 6). Here, the iron bis-phosphine cluster compounds are reacted with stoichiometric amounts of diphenyldisulphide (Ph2S2) in toluene at 65-70 °C for 30 min. The reactions afforded three products regardless of the n-value. Irrespective of the iron-containing reagent, one product is common to all reactions. A total of seven different compounds were isolated, six of which are new. The product formulations are: 1. the known compound [Fe2(SPh)2(CO)6] (common product); 2. [{Fe2(SPh)2(CO)5}Ph2P(CH2)nPPh2{Fe(CO)4}]; and 3. [{Fe2(SPh)2(CO)5}2Ph2P(CH2)nPPh2], (n=3, 4 and 6). Yields ranged 2-37% depending on the particular reactions. Reactions involving the {Fe3Fe} type species with [Ph2S2] (1:1 or 1:2 mole ratio) afforded predominantly phosphine sulphur compounds type (ii) above, whereas, when the {Fe3Fe3} type species were reacted (1:2 or 1:4 mole ratio), the major products were of type (iii) above.
