1,1'-Bis(diphenylphosphino)ferrocene
[CAS# 12150-46-8]

Identification

• Classification: Organic raw materials >> Organometallic compound >> Organic iron
• Name: 1,1'-Bis(diphenylphosphino)ferrocene
• Synonyms: 1,1'-Ferrocenebis(diphenylphosphine); 1,1'-Ferrocenediyl-bis(diphenylphosphine)
• Molecular Formula: C₃₄H₂₈FeP₂
• Molecular Weight: 554.39
• CAS Registry Number: 12150-46-8
• EC Number: 430-420-3
• SMILES: c1ccc(cc1)P(c2ccccc2)C34C5[Fe]3678912(C5C6C74)C3C8C9C1(C23)P(c1ccccc1)c1ccccc1

Properties

• Melting point: 181-183 °C

Safety Data

• Hazard Symbols: GHS06 Danger
• Risk Statements: H301
• Safety Statements: P261-P264-P270-P271-P280-P301+P310-P302+P352-P304+P340-P312-P330-P363-P405-P501

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Skin irritation	Skin Irrit.	2	H315
Eye irritation	Eye Irrit.	2	H319
Acute toxicity	Acute Tox.	4	H302
Specific target organ toxicity - single exposure	STOT SE	3	H335
Acute toxicity	Acute Tox.	4	H332
Acute toxicity	Acute Tox.	4	H312
Chronic hazardous to the aquatic environment	Aquatic Chronic	4	H413
Acute toxicity	Acute Tox.	3	H301
Chronic hazardous to the aquatic environment	Aquatic Chronic	3	H412
Eye irritation	Eye Irrit.	2A	H319

Discovery and Applications

1,1'-Bis(diphenylphosphino)ferrocene, commonly known as dppf, is a significant chemical compound that has become a cornerstone in the field of coordination chemistry and homogeneous catalysis. This compound features a ferrocene backbone, which consists of two cyclopentadienyl rings bound to an iron atom, with each ring substituted by a diphenylphosphino group. The unique structure of dppf makes it an exceptionally versatile ligand in various chemical processes.

The discovery of 1,1'-Bis(diphenylphosphino)ferrocene dates back to the mid-20th century during an era of intense exploration of organometallic compounds. Ferrocene, the parent compound of dppf, was discovered in 1951 and its sandwich-like structure quickly intrigued chemists. Building on this discovery, dppf was developed as a bidentate ligand, meaning it can bind to a metal center through both phosphorus atoms, creating a stable and flexible coordination environment. This feature is particularly useful in stabilizing metal complexes, which are crucial in catalysis.

In terms of application, 1,1'-Bis(diphenylphosphino)ferrocene is widely used as a ligand in transition metal-catalyzed reactions. Its most prominent role is in cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Heck reactions, which are fundamental in forming carbon-carbon bonds. These reactions are essential in the synthesis of pharmaceuticals, agrochemicals, and organic materials. The presence of the ferrocene unit not only provides stability but also enhances the electronic properties of the catalyst, making the reactions more efficient and selective.

Additionally, dppf’s versatility allows it to be used in a range of catalytic processes beyond cross-coupling. It has been employed in asymmetric synthesis, where the chiral environment it helps create can lead to the production of enantiomerically pure compounds, which are crucial in the development of drugs with specific biological activities. The compound’s ability to adjust the electronic and steric environment around the metal center also makes it a valuable tool in fine-tuning catalytic reactions.

Beyond catalysis, 1,1'-Bis(diphenylphosphino)ferrocene has found applications in materials science. Its coordination with metals can be utilized in creating new materials with interesting electronic, magnetic, or optical properties. These materials are being explored for use in sensors, electronic devices, and other advanced technologies.

In summary, 1,1'-Bis(diphenylphosphino)ferrocene is a key compound in modern chemistry, renowned for its role as a ligand in catalysis and its contributions to materials science. Its discovery has significantly impacted the way chemists approach the design of metal complexes and catalytic systems, making it a vital component in both academic research and industrial applications.

References

2009. 31P NMR study of the stoichiometry, stability and thermodynamics of complex formation between palladium(II) acetate and bis(diphenylphosphino)ferrocene. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy.
DOI: 10.1016/j.saa.2009.08.004

2014. Hydrogenase biomimetics: Fe2(CO)4(μ-dppf)(μ-pdt) (dppf = 1,1′-bis(diphenylphosphino)ferrocene) both a proton-reduction and hydrogen oxidation catalyst. Chemical Communications (Cambridge, England).
DOI: 10.1039/c3cc46456c

2007. Zirconium ion selective electrode based on bis(diphenylphosphino) ferrocene incorporated in a poly(vinyl chloride) matrix. Analytica Chimica Acta.
DOI: 10.1016/j.aca.2006.10.059