75249-92-2Relevant articles and documents
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.
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.
