Chlorobis(dppe)iron hydride

Chlorobis(dppe)iron hydride
Names
	IUPAC name Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II)
Identifiers
CAS Number	32490-70-3;
3D model (JSmol)	Interactive image;
	InChI InChI=1S/2C26H24P2.ClH.Fe.H/c21-5-13-23(14-6-1)27(24-15-7-2-8-16-24)21-22-28(25-17-9-3-10-18-25)26-19-11-4-12-20-26;;;/h21-20H,21-22H2;1H;;/q;;;+1;/p-1 Key: NSXBDVRBULAONI-UHFFFAOYSA-M;
	SMILES Cl[FeH-4]56([P+](c1ccccc1)(c2ccccc2)CC[P+]5(c3ccccc3)c4ccccc4)[P+](c1ccccc1)(c2ccccc2)CC[P+]6(c3ccccc3)c4ccccc4;
Properties
Chemical formula	C52H49ClFeP4
Molar mass	889.09
Appearance	red-violet solid
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

Chlorobis(dppe)iron hydride is a coordination complex with the formula HFeCl(dppe)₂, where dppe is the bidentate ligand 1,2-bis(diphenylphosphino)ethane. It is a red-violet solid. The compound has attracted much attention as a precursor to dihydrogen complexes.[1]

Structure

The complex exhibits octahedral molecular geometry. The chloride and hydride ligands are mutually trans.[2] 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 and reactions

The compound is synthesized according to this idealized reaction:[3]

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

"Top-view" of the structure of HFeCl(dppe)₂

In the course of this conversion, high-spin complex FeCl₂(dppe)₂ converts to low-spin HFeCl(dppe)₂.

The complex HFeCl[(dppe)₂ exhibits a number of reactions associated with the remaining Fe-Cl bond. Reaction of the complex with sodium borohydride gives the dihydride complex:

HFeCl(dppe)₂ + NaBH₄ → H₂Fe(dppe)₂ + NaCl + "BH₃"

Removal of chloride using sodium tetrafluorborate under and atmostphere of hydrogen or nitrogen gives the dinitrogen and dihydrogen complexes:[4]

HFeCl(dppe)₂ + NaBF₄ + N₂ → [HFe(N₂)(dppe)₂]BF4 + NaCl

HFeCl(dppe)₂ + NaBF₄ + H₂ → [HFe(H₂)(dppe)₂]BF4 + NaCl

References

Morris, R. H. (2008). "Dihydrogen, Dihydride and in Between: Nmr and Structural Properties of Iron Group Complexes". Coord. Chem. Rev. 2252 (21–22): 2381–2394. doi:10.1016/j.ccr.2008.01.010.
Lee, J.; Jung, G.; Lee, S. W. Structure of trans-chlorohydridobis(diphenylphosphinoethane)iron(II). Bull. Korean. Chem. 1998, 19, 267. ISSN 0253-2964
Giannoccaro, P.; Sacco, A. (1977). "Bis[ethylenebis(diphenylphosphine)]-Hydridoiron Complexes". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. 17. p. 69–71. doi:10.1002/9780470132487.ch19. ISBN 9780470132487.CS1 maint: uses authors parameter (link)
Bautista, M. T., Bynum, L. D., Schauer, C. K. (1996). "Synthesis of η²-Dihydrogen Complex, trans-{Fe(η²-H₂)(H)[1,2-bis(diphenylphosphino)ethane]₂}[BF₄]: An Experiment for an Advanced Inorganic Chemistry Laboratory Involving Synthesis and NMR Properties of an η²-H₂ Complex". Journal of Chemical Education. 73: 988–991. doi:10.1021/ed073p988.CS1 maint: uses authors parameter (link)

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[1] Morris, R. H. (2008). "Dihydrogen, Dihydride and in Between: Nmr and Structural Properties of Iron Group Complexes". Coord. Chem. Rev. 2252 (21–22): 2381–2394. doi:10.1016/j.ccr.2008.01.010.

[2] Lee, J.; Jung, G.; Lee, S. W. Structure of trans-chlorohydridobis(diphenylphosphinoethane)iron(II). Bull. Korean. Chem. 1998, 19, 267. ISSN 0253-2964

[3] Giannoccaro, P.; Sacco, A. (1977). "Bis[ethylenebis(diphenylphosphine)]-Hydridoiron Complexes". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. 17. p. 69–71. doi:10.1002/9780470132487.ch19. ISBN 9780470132487.CS1 maint: uses authors parameter (link)

[4] Bautista, M. T., Bynum, L. D., Schauer, C. K. (1996). "Synthesis of η²-Dihydrogen Complex, trans-{Fe(η²-H₂)(H)[1,2-bis(diphenylphosphino)ethane]₂}[BF₄]: An Experiment for an Advanced Inorganic Chemistry Laboratory Involving Synthesis and NMR Properties of an η²-H₂ Complex". Journal of Chemical Education. 73: 988–991. doi:10.1021/ed073p988.CS1 maint: uses authors parameter (link)