100447-70-9Relevant articles and documents
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)
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.
MULTIPLE REACTION PATHWAYS IN THE REACTIONS OF CARBONYLFERRATE ANIONS WITH CHALCOGENS, AND WITH CHALCOGEN-CONTAINING ANIONS
Glidewell, Christopher
, p. 73 - 78 (1985)
The reactions of - or - with either sulphite or polysulfide all yield a mixture of Fe2S2(CO)6, Fe3S2(CO)9, Fe3S(CO)10 and Fe3S(CO)9(SO), together with Fe3(CO)12 in the reactions with sulphite.Fe2S2(CO)6 readily undergoes cluster expansion with - to yield Fe3S2(CO)9, but further reaction to give Fe3S(CO)10, or reconversion to Fe2S2(CO)6 is not possible.In contrast, - with selenite yields Fe3S2(CO)9 only, but - yields not only Fe3Se2(CO)9 but also Fe2Se2(CO)6 and Fe3(CO)12.With high molar ratios of elemental sulphur or selenium, - yields pure Fe2E2(CO)6 (E = S or Se) but with an equimolar amount sulphur a mixture of Fe3S2(CO)9, Fe3(CO)12, Fe3S(CO)10 and Fe3S(CO)9(SO), with no Fe2S2(CO)6, is obtained: use of an equimolar amount of selenium yieds both Fe2Se2(CO)6 and Fe3Se2(CO)9.The formation and interconversions of iron-chalcogen carbonyl clusters are discussed.
Synthesis of trinuclear mixed-metal clusters Os2Fe(CO)10L2 (L = OH, I, CO). The crystal structures of Os2Fe(CO)10(μ-OH)2 and Os2Fe(CO)12 · 0.41Os3(CO)12
Maksakov,Kirin,Virovets,Podberezskaya,Semyannikov
, p. 57 - 62 (2007/10/03)
The heterometallic clusters Os2Fe(CO)10(μ-X)2 (X = OH, I) were obtained from the binuclear osmium complexes Os2(CO)6Xn (X = Cl, n = 4; X = I, n = 2). The structure of Os2Fe(CO)10(μ-OH)2 was determined by a single-crystal X-ray diffraction analysis. The crystal is triclinic and crystallizes in the space group P1 and a = 14.009(6), b = 13.330(4), c = 9.511(2) A, α = 103.69(2), β = 81.83(3), γ = 102.22(3)°, V = 1699(1) A3, Z = 4, Dcalc = 2.969 g cm-3, R = 0.093 for 2359 independent reflections (Fo > 6σ(Fo)). The cluster consists of an open triangular OsFeOs metal core with no Os-Os bond. The bridging OH groups are coordinated semiaxially and span the Os-Os edge. On heating in the presence of an excess of Fe2(CO)9, the Os2Fe(CO)10(μ-I)2 cluster is converted to Os2Fe(CO)12. The co-crystallate Os2Fe(CO)12 · 0.41Os3(CO)12 was isolated from the solution of Os2Fe(CO)10(μ-I)2, as the product of decomposition of the initial cluster. It crystallizes in the monoclinic system, space group P21/n, with a = 8.056(2), b = 14.743(2), c = 14.520(2) A, β = 100.62(1)°, V = 1695.0(5) A3, Z = 4, Dcalc = 3.179 g cm-3 and R = 0.0250 for 1997 independent reflections (Fo > 4σ(Fo)).
