Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II)

Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II)
Names
IUPAC name
Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II)
Identifiers
32490-70-3
Properties
C52H49P4ClFe
Molar mass 889.09
Appearance red-violet crystal
Melting point 195 °C (383 °F; 468 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II) is a coordination complex with the formula HFeCl[(C6H5)2PCH2CH2P(C6H5)2]2 or HFeCl(dppe)2, where dppe is the ligand 1,2-bis(diphenylphosphino)ethane.[1] The trans confirmation is the most often reported structure, and the compound is a red-violet crystalline solid. The compound is an electron-rich, coordinatively unsaturated complex where the iron metal is in a low oxidation state.[2] It is typical used as the starting material for a number of iron complexes containing the Fe[(C6H5)2PCH2CH2P(C6H5)2]2 moiety.

Structure

The coordination sphere of the iron metal can be described as octahedral. The chloride and hydride ligands are trans, giving a D4h ideal rotation axis that passes through the Fe, Cl, and H atoms.[3] This axis is perpendicular to the equatorial plane defined by the four phosphorus atoms, through which the Fe metal lies slightly above. This suggests that the four phosphorus nuclei are equivalent. The bond distances between the iron metal atom and the coordinating ligands are given by the following.

Bond Bond Distance
Fe-P1 2.238
Fe-P2 2.256
Fe-P3 2.236
Fe-P4 2.255
Fe-Cl 2.404
Fe-H 1.313

Synthesis

The compound is synthesized according to the balanced reaction.

FeCl2 + 2 (C6H5)2PCH2CH2P(C6H5)2 + Na[BH4] → NaCl + ½ B2H6 + HFeCl[(C6H5)2PCH2CH2P(C6H5)2]2

References

  1. Giannoccaro, P.; Sacco, A. "Bis[ethylenebis(diphenylphosphine)]-Hydridoiron Complexes" Inorg. Synth. 1977, volume 17, p. 69. doi:10.1002/9780470132487.ch19
  2. Grushin, V. V. Reductive elimination of hydrogen chloride from chloro hydrido transition metal complexes: an efficient and simple method for generation of electron-rich, coordinatively unsaturated, reactive intermediates. Acc. Chem. Res. 1993, 26, 279. doi:10.1021/ar00029a009
  3. Lee, J.; Jung, G.; Lee, S. W. Structure of trans-chlorohydridobis(diphenylphosphinoethane)iron(II). Bull. Korean. Chem. 1998, 19, 267. ISSN 0253-2964
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