The synthesis and structure from IR and NMR data of the complex (μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCCOOCH3) are described, and its reactivity toward H+ is studied. Protonation gives a chelated (C, O) 1, 2-bis(carbomethoxy)ethylene complex in which the added proton is cis to the carbon-bonded iron atom. The structure of the product has been established by a crystal structure determination of [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CEI3COOCCHCOOCH3)][B(C6H5)4]. In this complex each iron atom is octahedrally coordinated to two bridging sulfur atoms of the methylthiolato groups, two phosphine ligands trans to the sulfur atoms, one carbonyl group, and a vinylic carbon atom for one iron atom and an oxygen atom of the α-carbonyl ester group for the other. The compound crystallizes with 4 formula units in the monoclinic space group C52h-P21/c in a cell of dimensions a = 10.716 (4) Å, b = 30.227 (11) Å, c = 16, 346 (5) Å, and β = 102.75 (1)°. On the basis of 5856 unique reflections, the structure was refined by full-matrix least-squares techniques to conventional indices (on F) of R = 0.050 and Rw = 0.057. The Fe-Fe separation of 3.452 (1) Å and the dihedral angle around the sulfur atoms of 157.8° lead to the widest spacing thus far found for this type of dinuclear, sulfur-bridged iron complex.
|Original language||English (US)|
|Number of pages||6|
|State||Published - 1980|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry