76419-41-5Relevant academic research and scientific papers
Reduction of the group 2B tetracarbonylferrates in Lewis bases. Synthesis, characterization, and structural features of the (Na{THF}2)+2[M′(Fe(CO)4) 2]2-(M′ = Zn, Cd, and Hg) series
Sosinsky, Barrie A.,Shong, Robert G.,Fitzgerald, Brian J.,Norem, Nathan,O'Rourke, Carol
, p. 3124 - 3129 (2008/10/08)
In the presence of Lewis bases [M′Fe(CO)4]x complexes (I; M′ = Zn, Cd, and Hg) undergo mild stepwise reduction to give first the kinetically stable [M′(Fe(CO)4)2]2- (II) and subsequently [Fe2(CO)8]2- (III). The mechanism for base reduction is considered in terms of competing base reactions. The solid-state structures of (Na{THF}2)+2[M′(Fe(CO)4) 2]2- (IIa-c; M′ = Zn, Cd, and Hg, respectively) have been determined and are directly related to their solution-state infrared spectra with distortions in the dianions retained in both states. The results of our structure determination on (Na{THF}2)+2- [Zn(Fe(CO)4)2]2- have been described in a previous communication. Crystals of the Hg analogue form in the same space group, and C2h site symmetry is also imposed on the complex anion. Cell dimensions for IIc are a = 12.39 (3) ?, b = 8.54 (1) ?, c = 16.01 (1) ?, β = 105.5 (2)°, and V = 1636 ?3. The geometry about the Fe atoms is that of a Fe(CO)4 tetrahedron with the Fe-Hg bond capping one face. Bonds between carbonyl oxygen atoms of the anion and the Na(THF)2+ cations result in an extended oligomeric structure in the solid state. 57Fe M?ssbauer spectra recorded on [M′(Fe(CO)4)2]2-gave the following parameters: M′ = Zn, δ = 0.416, Δ = 1.429 mm s-1; M′ = Cd, δ = 0.232 and 1.192, Δ = 1.112 and 0.808 mm s-1, respectively (relative to SNP). IIb has two magnetically distinct iron atoms. IIa does not undergo facile reaction toward mercury and is sluggishly reactive toward NiCl2, yielding III. Reaction of IIa with HgCl2 yields the transmetalated product [Fe(CO)4(HgCl)2], whereas reaction of IIa with Hg2Cl2 yields only III with small amounts of IIa and IIc.
