15634-63-6Relevant articles and documents
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
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.
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.
Dyk, Marthie M. van,Rooyen, Petrus H. van,Lotz, Simon
, p. 167 - 172 (1989)
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.
