1,1'-Bis(diphenylphosphino)ferrocene

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1,1′-Bis(diphenylphosphino)­ferrocene
Names
Preferred IUPAC name
(Ferrocene-1,1′-diyl)bis(diphenylphosphane)
Other names
1,1′-Bis(diphenylphosphino)ferrocene, 1,1′-ferrocenediylbis(diphenylphosphine), Dppf, 1,1′-ferrocenebis(diphenylphosphine), 1,1′-bis(diphenylphosphanyl)ferrocene
Identifiers
3D model (
JSmol
)
ChEBI
ChemSpider
ECHA InfoCard
 100.167.773 Edit this at Wikidata
EC Number
  • 640-119-0
24075
UNII
  • InChI=1S/2C17H14P.Fe/c2*1-3-9-15(10-4-1)18(17-13-7-8-14-17)16-11-5-2-6-12-16;/h2*1-14H; checkY
    Key: HPXNTHKXCYMIJL-UHFFFAOYSA-N checkY
  • InChI=1/2C17H14P.Fe/c2*1-3-9-15(10-4-1)18(17- -13-7-8-14-17)16-11-5-2-6-12-16;/h2*1-14H;/q2*-1;+2
    Key: HPXNTHKXCYMIJL-UHFFFAOYSA-N
  • InChI=1/2C17H14P.Fe/c2*1-3-9-15(10-4-1)18(17-13-7-8-14-17)16-11-5-2-6-12-16;/h2*1-14H;/rC34H28FeP2/c1-5-13-21(14-6-1)36(22-15-7-2-8-16-22)33-29-25-26-30(33)35(25,26,29,33)27-28(35)32(35)34(35,31(27)35)37(23-17-9-3-10-18-23)24-19-11-4-12-20-24/h1-20,25-32H
    Key: HPXNTHKXCYMIJL-KDKHWAOJAX
  • c1ccc(cc1)P(c2ccccc2)C34C5[Fe]3678912(C5C6C74)C3C8C9C1(C23)P(c1ccccc1)c1ccccc1
  • C1=CC=C(C=C1)P([C-]2C=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P([C-]2C=CC=C2)C3=CC=CC=C3.[Fe+2]
Properties
C34H28FeP2
Molar mass 554.391
Melting point 181 to 183 °C (358 to 361 °F; 454 to 456 K)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Toxic
GHS labelling:
GHS07: Exclamation markGHS08: Health hazard
Warning
H302, H312, H315, H319, H332
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

1,1′-Bis(diphenylphosphino)ferrocene, commonly abbreviated dppf, is an

1,2-bis(diphenylphosphino)ethane
(dppe).

Preparation

This compound is commercially available. It may be prepared by treating

dilithioferrocene with chlorodiphenylphosphine:[1]

Fe(C5H4Li)2 + 2 ClPPh2 → Fe(C5H4PPh2)2 + 2 LiCl

The dilithiation of

TMEDA
. Many related ligands can be made in this way. The Fe center is typically not involved in the behavior of the ligand.

Reactions

Dppf readily forms metal complexes.

palladium dichloride:[2] Substitution of the phenyl substituents in dppf leads to derivatives with modified donor-acceptor properties at the phosphorus atoms.[3]

dppf + PdCl2(RCN)2 → (dppf)PdCl2 + 2 RCN (RCN = acetonitrile or benzonitrile)
Structure of the complex PtCl2(dppf)

Another example of dppf in homogeneous catalysis is provided by the air- and moisture-stable Ni(II) precatalyst [(dppf)Ni(cinnamyl)Cl. It promotes Suzuki-Miyuara cross-coupling of heteroaryl boronic acids with nitrogen- and sulfur-containing heteroaryl halides.[4]

Synthesis of [(dppf)Ni(cinnamyl)Cl)]

Another dppf-based catalyst is (dppf)Ni(o-tolyl)Cl, can be prepared from ligand exchange with (PPh3)2Ni(o-tolyl)Cl. It promotes the amination of aryl chlorides, sulfamates, mesylates, and triflates.[5]

Synthesis of (dppf)Ni(o-tolyl)Cl

See also

  • Diphosphines
  • borrowing hydrogen
    catalysis

References

  1. ISBN 978-3-527-32472-9
    .
  2. ^
    doi:10.1021/ed086p1412
    .
  3. doi:10.1016/j.ccr.2021.213850
    .
  4. PMID 23136047
    .
  5. PMID 24283652
    .
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