Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH3)Fe(CO)(P(CH3)3)2]2. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCHCOOCH3)][B(C6H5)4]

J. J. Bonnet, R. Mathieu, James A Ibers

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Abstract

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 C5 2h-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 languageEnglish (US)
Pages (from-to)2448-2453
Number of pages6
JournalInorganic Chemistry
Volume19
Issue number8
DOIs
StatePublished - Jan 1 1980

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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