75249-93-3Relevant academic research and scientific papers
Chemistry of (μ-dithio)bis(tricarbonyliron), an inorganic mimic of organic disulfides. 3. Reaction with low-valent metal compounds and some interesting isolobal analogies involving the products
Cowie, Martin,DeKock, Roger L.,Wagenmaker, Timothy R.,Seyferth, Dietmar,Henderson, Richard S.,Gallagher, Michael K.
, p. 119 - 132 (2008/10/08)
The analogy between (μ-S2)Fe2(CO)6 and organic disulfides extends to reactions with low-valent metal species. The following zerovalent metal phosphine complexes and (organo)metal carbonyls react with (μ-S2)Fe2(CO)6: (Ph3P)4Pt, (Ph3P)3PdCO, (diphos)Ni(CO)2, (η5-C5H5)2Ti(CO)2, (η5-C5H5)Co(CO)2, (η5-C5Me5)Co(CO)2, [(η5-C5H5)Co(μ-CO)]2, Co2(CO)8, Fe2(CO)9, Fe(CO)2(NO)2. In all cases, initial attack appears to occur at the S-S bond of (μ-S2)Fe2(CO)6. Two products of these reactions, (η5-C5Me5)Co(μ3-S) 2Fe2(CO)6 and [(η5-C5Me5)Co(μ-CO)] 2(μ3-S)2Fe2(CO)6, have been structurally characterized by X-ray crystallography. The former crystallizes in the orthorhombic space group P212121 with a = 8.848 (5) A?, b = 12.571 (3) A?, c = 18.707 (3) A?, and Z = 4. Refinement has converged at R = 0.058 and Rw = 0.051 based on 2031 unique observations (NO) and 244 parameters varied (NV). This heteronuclear cluster has a structure in which the Co atom is sandwiched between the C5Me5 group and the four-membered, heteroatom ring of the (μ-S)2Fe2(CO)6 moiety, which in the observed geometry, is isolobal with cyclobutadiene. Cobalt is bonded to the Fe and S atoms, but there is no Fe-Fe bond. A rationalization for the observed structure, based on Fenske-Hall Calculations, is presented. The structural parameters for the second species are as follows: monoclinic space group P21/m, a = 10.712 (1) A?, b = 14.837 (2) A?, c = 10.8215 (9) A?, β = 115.537 (8)°, Z = 2, R = 0.033, Rw = 0.040, NO = 2409, and NV = 202. This structure has resulted from the apparent insertion of the (η5-C5Me5)2Co 2(μ-CO)2 moiety into the S-S bond of the Fe2(μ2-S2)(CO)6 butterfly , such that the two fragments are linked by two Co-S bonds. The Co-Co bond lies essentially parallel to the S-S axis and perpendicular to the Fe-Fe bond.
SYNTHESIS OF HETEROMETALLIC CLUSTER COMPOUNDS FROM Fe3(μ3-Te)2(CO)9 AND COMPARISONS WITH ANALOGOUS SULFIDE CLUSTERS
Bogdan, Leonard E.,Lesch, David A.,Rauchfuss, Thomas B.
, p. 429 - 438 (2007/10/02)
Fe3Te2(CO)9 is shown to be a useful precursor to a variety of heterometallic carbonyl clusters in reactions which appear to proceed via the intermediacy of Fe2(Te2)(CO)6.Fe3Te2(CO)9 decomposed in polar solvents to give Fe2(Te2)(CO)6 which could be dimerized to Fe4Te4(CO)12.Fe3Te2(CO)9 reacted with C5H5Co(CO)2 and Pt(C2H4)(PPh3)2 to give good yields of (C5H5Co)Fe2Te2(CO)7 and Fe2PtTe2(CO)6(PPh3)2, respectively. (C5H5Co)Fe2Te2(CO)7 underwent reversible decarbonylation to give a mixture of two isomers of (C5H5Co)Fe2Te2(CO)6 as established by 125Te NMR spectroscopy.Upon reaction with Co2(CO)8, Fe3Te2(CO)9 gave Co2FeTe(CO)9 or Co4Te2(CO)11 depending on the reaction conditions.Co4Te2(CO)11, like Fe3Te2(CO)10 and (C5H5Co)Fe2Te2(CO)7, can be reversibly decarbonylated.The assembly of Co2FeTe(CO)9 may be mechanistically related to the conversion of Fe2(S2)(CO)6 to FeCo2S(CO)9 which was found to proceed via Co2Fe2S2(CO)11.Alternatively, Co2Fe2S2(CO)11 reacted photochemically with 2 to give the known, chiral cluster (C5H5Mo)CoFeS(CO)8.While Fe2(Te2)(CO)6 thermally dimerized to Fe4Te4(CO)12, Fe2(S2)(CO)6 gave the analogous dimer only upon photolysis.In contrast to the stability of (C5H5Co)Fe2Te2(CO)7, the reaction of C5H5Co(CO)2 with Fe2(S2)(CO)6 gave only (C5H5Co)Fe2S2(CO)6 which is proposed to be structurally related to Fe3S2(CO)9 and not (C5H5Co)3S2 or Fe2PtS2(CO)6(PPh3)2.
Fe2(μ-E2)(CO)6 (E = S, Se, and Te) as Reagents for the Preparation of Mixed-Metal Chalcogenide Clusters
Day, Victor W.,Lesch, David A.,Rauchfuss, Thomas B.
, p. 1290 - 1295 (2007/10/02)
The compounds Fe2(μ-E2)(CO)6, where E = S, Se, and Te, react efficiently with Pt(PPh3)2C2H4 to afford the new heterometallic clusters, (CO)6Fe2(μ-E)2Pt(PPh3)2.This reaction formally involves the homolytic cleavage of the E-E bond in the μ-E2 precursor complexes and represents a novel route to mixed-metal clusters. 13P NMR of (PPh3)(CO)5Fe2(μ-S)2Pt(PPH3)2 (prepared from Fe2(μ-S2)(CO)5(PPh3) indicates that the plane of the Pt coordination sphere is perpendicular to the iron-iron vector.The structure of (CO)6Fe2(μ3-Se)2Pt(PPh3)2 was determined by conventional X-ray crystallographic techniques.The crystals were monoclinic with a = 10.944(2) Angstroem, b = 16.321(3) Angstroem, c = 23.135(4) Angstroem, β = 94.68(1) deg, Z = 4; the space group is P21/n.Conventional full-matrix least-squares refinement with nonhydrogen atoms anisotropic and fixed hydrogen atoms isotropic gave R1 = 0.037 and R2 = 0.040 for 7119 reflections having 2θ Mo Kα/ 3?(I).The structure consists of an isosceles triangle of metal atoms tethered by two capping μ3-Se moieties.The two Fe(CO)3 units are mutually bonded, and this fragment closely resembles Fe2(μ-Se2)(CO)6 with an expanded Se-Se vector.We reconcile the reactivity of these μ-E2 compounds and the chemical dormancy of species such as Ph2Te2 and monometallic S2 complexes as being both electronic and steric (ring strain) in origin.
(μ-DITHIO)BIS(TRICARBONYLIRON) AS AN ORGANIC DISULFIDE MIMIC: INSERTION OF LOW-VALENT METAL SPECIES INTO THE SULFUR-SULFUR BOND
Seyferth, Dietmar,Henderson, Richard S.,Gallagher, Michael K.
, p. C75 - C78 (2007/10/02)
Low valent metal species: (Ph2PCH2CH2PPh2)Ni0, (Ph3P)2Pd0, (Ph3P)2Pt0, η5-C5H5CoI and (CH3)2SnII insert into the S-S bond of (μ-S2)Fe2(CO)6 under mild conditions.Identical products were obtained by reactions of the dianion, 2- with the corresponding metal chlorides.
DIRECTED SYNTHESIS OF MIXED METAL CHALCOGENIDE CLUSTERS: OXIDATIVE ADDITIONS OF Fe2(μ2-E2)(CO)6 (E = S, Se, Te)
Lesch, David A.,Rauchfuss, Thomas B.
, p. C6 - C8 (2007/10/02)
The reaction of Fe2(μ2-E2)(CO)6 with M(PPh3)2(C2H4) affords quantitative yields of (CO)6Fe2(μ3-E)2M(PPh3)2 (E=S, Se, Te; M=Pt, Pd), which were characterized by analytical data, molecular weight measurements, IR, and heteronuclear NMR.
