Chlorobis(dppe)iron hydride

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Chlorobis(dppe)iron hydride
HFeCl dppe 2.svg
WEQGOOsideon.png
Names
IUPAC name
Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II)
Identifiers
3D model (JSmol)
  • InChI=1S/2C26H24P2.ClH.Fe.H/c2*1-5-13-23(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;;;/h2*1-20H,21-22H2;1H;;/q;;;+1;/p-1
    Key: NSXBDVRBULAONI-UHFFFAOYSA-M
  • Cl[FeH-4]56([P+](c1ccccc1)(c2ccccc2)CC[P+]5(c3ccccc3)c4ccccc4)[P+](c1ccccc1)(c2ccccc2)CC[P+]6(c3ccccc3)c4ccccc4
Properties
C52H49ClFeP4
Molar mass 889.09
Appearancered-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).

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]

Contents

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:

BondBond distance
Fe-P12.238
Fe-P22.256
Fe-P32.236
Fe-P42.255
Fe-Cl2.404
Fe-H1.313

Synthesis and reactions

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

FeCl2 + 2 dppe + Na[BH4] → NaCl + ½ B2H6 + HFeCl(dppe)2
"Top-view" of the structure of HFeCl(dppe)2 WEQGOOtopdown.png
"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

Related Research Articles

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<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

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Iron(II) hydride, systematically named iron dihydride and poly(dihydridoiron) is solid inorganic compound with the chemical formula (FeH
2
)
n
(also written ([FeH
2
]
)n or FeH
2
). ). It is kinetically unstable at ambient temperature, and as such, little is known about its bulk properties. However, it is known as a black, amorphous powder, which was synthesised for the first time in 2014.

<span class="mw-page-title-main">Bis(dinitrogen)bis(1,2-bis(diphenylphosphino)ethane)molybdenum(0)</span> Chemical compound

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<span class="mw-page-title-main">Dichloro(1,2-bis(diphenylphosphino)ethane)nickel</span> Chemical compound

Dichloro[1,2-bis(diphenylphosphino)ethane]nickel is a coordination complex with the formula NiCl2(dppe); where dppe is the diphosphine 1,2-bis(diphenylphosphino)ethane. It is used as a reagent and as a catalyst. The compound is a bright orange-red diamagnetic solid. The complex adopts a square planar geometry.

References

  1. Morris RH (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. pp. 69–71. doi:10.1002/9780470132487.ch19. ISBN   9780470132487.{{cite book}}: |journal= ignored (help)
  4. Bautista MT, Bynum LD, Schauer CK (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 (10): 988–991. doi:10.1021/ed073p988.