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|Section1={{Chembox Identifiers
|Section1={{Chembox Identifiers
| CASNo = 32490-70-3
| CASNo = 32490-70-3
| PubChem =
| PubChem = 165365653
| SMILES = Cl[FeH-4]56([P+](c1ccccc1)(c2ccccc2)CC[P+]5(c3ccccc3)c4ccccc4)[P+](c1ccccc1)(c2ccccc2)CC[P+]6(c3ccccc3)c4ccccc4
| SMILES = }}
| StdInChI=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
| StdInChIKey=NSXBDVRBULAONI-UHFFFAOYSA-M
}}
|Section2={{Chembox Properties
|Section2={{Chembox Properties
| C=52|H=49|P=4|Cl=1|Fe=1
| C=52|H=49|P=4|Cl=1|Fe=1
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}}
}}
}}
}}
'''Chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II)''' is a coordination complex with the formula <sub>2</sub>, where [[dppe]] is the ligand 1,2-bis(diphenylphosphino)ethane.<ref>Giannoccaro, P.; Sacco, A. "Bis[ethylenebis(diphenylphosphine)]-Hydridoiron Complexes" Inorg. Synth. 1977, volume 17, p. 69. {{DOI|10.1002/9780470132487.ch19}}</ref> It is a red-violet solid.<ref>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, and reactive intermediates. Acc. Chem. Res. 1993, 26, 279. {{DOI|10.1021/ar00029a009}}</ref>
'''Chlorobis(dppe)iron hydride''' is a [[coordination complex]] with the formula HFeCl(dppe)<sub>2</sub>, 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 complex]]es.<ref>{{cite journal |vauthors=Morris RH |title=Dihydrogen, Dihydride and in Between: Nmr and Structural Properties of Iron Group Complexes |journal=Coord. Chem. Rev. |year=2008 |volume=2252 |issue=21–22 |pages=2381–2394 |doi=10.1016/j.ccr.2008.01.010}}</ref>


==Structure==
==Structure==
The coordination sphere of the iron metal can be described as octahedral. The chloride and hydride ligands are mutually trans.<ref>Lee, J.; Jung, G.; Lee, S. W. Structure of trans-chlorohydridobis(diphenylphosphinoethane)iron(II). Bull. Korean. Chem. 1998, 19, 267. {{ISSN|0253-2964}}</ref> The bond distances between the iron metal atom and the coordinating ligands are given by the following:
The complex exhibits [[octahedral molecular geometry]]. The chloride and hydride ligands are mutually trans.<ref>Lee, J.; Jung, G.; Lee, S. W. Structure of trans-chlorohydridobis(diphenylphosphinoethane)iron(II). Bull. Korean. Chem. 1998, 19, 267. {{ISSN|0253-2964}}</ref> The bond distances between the iron metal atom and the coordinating ligands are given by the following:
{|class="toccolours" border="1" style="margin: 1em; border-collapse: collapse;"
{|class="toccolours" border="1" style="margin: 1em; border-collapse: collapse;"
|-
|-
| Bond || Bond Distance
| Bond || Bond distance
|-
|-
| Fe-P<sub>1</sub> || 2.238
| Fe-P<sub>1</sub> || 2.238
Line 47: Line 50:
|}
|}
==Synthesis and reactions==
==Synthesis and reactions==
The compound is synthesized according to the following idealized reaction:<ref>{{cite book|author1=Giannoccaro, P. |author2=Sacco, A. |title=Inorganic Syntheses |chapter=Bis&#91;Ethylenebis(Diphenylphosphine)&#93;-Hydridoiron Complexes |journal=Inorg. Synth.|year=1977|volume=17|pages=69–71|doi=10.1002/9780470132487.ch19|isbn=9780470132487 }}</ref>
The compound is synthesized according to this idealized reaction:
:FeCl<sub>2</sub> + 2 dppe + Na[BH<sub>4</sub>] → NaCl + ½ B<sub>2</sub>H<sub>6</sub> + HFeCl[(dppe)<sub>2</sub>
:FeCl<sub>2</sub> + 2 dppe + Na[BH<sub>4</sub>] → NaCl + ½ B<sub>2</sub>H<sub>6</sub> + HFeCl(dppe)<sub>2</sub>
[[File:WEQGOOtopdown.png|thumb|left|144 px|Alternative view of the structure of HFeCl(dppe)<sub>2</sub>.]]
[[File:WEQGOOtopdown.png|thumb|left|144 px|"Top-view" of the structure of HFeCl(dppe)<sub>2</sub>]]
In the course of this conversion, high-spin complex FeCl<sub>2</sub>(dppe)<sub>2</sub> converts to low-spin HFeCl(dppe)<sub>2</sub>.


Reaction of the complex with [[sodium borohydride]] gives the dihydride complex:
The complex HFeCl[(dppe)<sub>2</sub> 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))<sub>2</sub> + NaBH<sub>4</sub> → H<sub>2</sub>)Fe(dppe))<sub>2</sub> + NaCl + "BH<sub>3</sub>"
:HFeCl(dppe)<sub>2</sub> + NaBH<sub>4</sub> → H<sub>2</sub>Fe(dppe)<sub>2</sub> + NaCl + "BH<sub>3</sub>"


Reaction of the complex with [[sodium tetrafluorborate under and atmostphere of hydrogen gives the [[dihydrogen complex]]:<ref>{{cite journal|authors=Bautista, M. T., Bynum, L. D., Schauer]], C. K.|title=Synthesis of η2-Dihydrogen Complex, trans-{Fe(η<sup>2</sup>-H<sub>2</sub>)(H)[1,2-bis(diphenylphosphino)-ethane]<sub>2</sub>}[BF<sub>4</sub>]: An Experiment for an Advanced Inorganic Chemistry Laboratory Involving Synthesis and NMR Properties of an η2-H2 Complex|journal=Journal of Chemical Education|year=1996|volume=73|page=988|doi=10.1021/ed073p988.}}</ref>
Removal of chloride using sodium tetrafluorborate under and atmostphere of hydrogen or nitrogen gives the [[dinitrogen complex|dinitrogen]] and [[dihydrogen complex]]es:<ref>{{cite journal|vauthors=Bautista MT, Bynum LD, Schauer CK |title=Synthesis of η<sup>2</sup>-Dihydrogen Complex, ''trans''-<nowiki>{</nowiki>Fe(η<sup>2</sup>-H<sub>2</sub>)(H)[1,2-bis(diphenylphosphino)ethane]<sub>2</sub><nowiki>}</nowiki>[BF<sub>4</sub>]: An Experiment for an Advanced Inorganic Chemistry Laboratory Involving Synthesis and NMR Properties of an η<sup>2</sup>-H<sub>2</sub> Complex |journal=Journal of Chemical Education |year=1996 |volume=73 |issue=10 |pages=988–991 |doi=10.1021/ed073p988}}</ref>
:HFeCl(dppe))<sub>2</sub> + NaBF<sub>4</sub> → [HFe(H<sub>2</sub>)(dppe))<sub>2</sub>]BF4 + NaBF<sub>4</sub>
:HFeCl(dppe)<sub>2</sub> + NaBF<sub>4</sub> + N<sub>2</sub> → [HFe(N<sub>2</sub>)(dppe)<sub>2</sub>]BF<sub>4</sub> + NaCl
:HFeCl(dppe)<sub>2</sub> + NaBF<sub>4</sub> + H<sub>2</sub> → [HFe(H<sub>2</sub>)(dppe)<sub>2</sub>]BF<sub>4</sub> + NaCl


==References==
==References==
<references />
<references />


[[Category:Metal hydrides]]
[[Category:Hydrido complexes]]
[[Category:Iron compounds]]
[[Category:Iron(II) compounds]]
[[Category:Chloro complexes]]
[[Category:Chloro complexes]]
[[Category:Phosphine complexes]]
[[Category:Phosphine complexes]]
[[Category:Iron complexes]]
[[Category:1,2-Ethanediyl compounds]]

Latest revision as of 07:06, 30 November 2024

Chlorobis(dppe)iron hydride
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
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).

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

[edit]

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

[edit]

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

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

[edit]
  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. Vol. 17. 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.
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