58204-17-4Relevant academic research and scientific papers
The bridging sulfide anion reactivity of Roussin's red salt
Seyferth, Dietmar,Gallagher, Michael K.,Cowie, Martin
, p. 539 - 548 (2008/10/08)
Reactions of Roussin's red sodium salt with organic halides gave (μ-RS)2Fe2(NO)4 (two isomers) in good yield, while reactions with R3SnX (R = Ph, Me), Ph3PbBr, and RHgX (R = Ph, Me) and with [η5-C5H5Fe(CO)2THF]BF 4 yielded the expected organometal derivatives. Reactions with (OC)4FeI2 and CpCo(CO)I2 (Cp = η5-C5H6 and η5-C5Me5) gave metal sulfur cluster complexes in low yield. The structure of one of these, (μ3-S)2(η5-C5Me 5Co)2[(ON)2Fe], was determined by X-ray diffraction. Other methods for the preparation of organic and organometallic derivatives of Roussin's red salt were investigated: nitrosylation of the corresponding hexacarbonyl compounds; reaction of (μ-Me3SnS)2Fe2(NO)4 with halides; piperidine-induced Michael additions of (μ-HS)2Fe2(NO)4 to α,β-unsaturated olefins. The complex (η5-C5Me5)2Co 2(μ-S)2Fe(NO)2 crystallizes in the space group C2/c with a = 32.951 (5) A?, b = 8.755 (1) A?, c = 17.619 (2) A?, β = 112.23 (1)°, and Z = 8. Refinement has converged at R = 0.028 and Rw = 0.039 for 262 variables and 3662 unique observations. The structure consists of a trigonal-bipyramidal Co2FeS2 core in which the Co2Fe triangle is capped above and below by triply bridging sulfido groups. One C5Me5 group is bound in an η5-fashion to each Co center and the two partially bent nitrosyls (average Fe-N-O angle = 159.8°) are bound to Fe.
