1,3-Bis(diphenylphosphino)propane
[CAS# 6737-42-4]

Identification

• Classification: Organic raw materials >> Organic phosphine compound
• Name: 1,3-Bis(diphenylphosphino)propane
• Synonyms: Propane-1,3-diylbis(diphenylphosphine)
• Molecular Formula: C₂₇H₂₆P₂
• Molecular Weight: 412.45
• CAS Registry Number: 6737-42-4
• EC Number: 229-791-2
• SMILES: C1=CC=C(C=C1)P(CCCP(C2=CC=CC=C2)C3=CC=CC=C3)C4=CC=CC=C4

Properties

• Melting point: 57-63 ºC
• Water solubility: insoluble

Safety Data

• Hazard Symbols: GHS07;GHS09 Warning
• Hazard Statements: H302-H315-H317-H319-H335-H400-H410
• Precautionary Statements: P261-P264-P264+P265-P270-P271-P272-P273-P280-P301+P317-P302+P352-P304+P340-P305+P351+P338-P319-P321-P330-P332+P317-P333+P317-P337+P317-P362+P364-P391-P403+P233-P405-P501

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Eye irritation	Eye Irrit.	2	H319
Skin irritation	Skin Irrit.	2	H315
Specific target organ toxicity - single exposure	STOT SE	3	H335
Chronic hazardous to the aquatic environment	Aquatic Chronic	1	H410
Skin sensitization	Skin Sens.	1	H317
Acute toxicity	Acute Tox.	4	H302
Acute hazardous to the aquatic environment	Aquatic Acute	1	H400
Chronic hazardous to the aquatic environment	Aquatic Chronic	4	H413

Discovory and Applicatios

1,3-Bis(diphenylphosphino)propane, commonly abbreviated as dppp, is a bidentate ligand that has played a significant role in the field of organometallic chemistry and homogeneous catalysis. The molecule consists of a propane backbone with two diphenylphosphino groups attached to the first and third carbon atoms. This structure allows dppp to chelate metal centers, forming stable complexes that are widely utilized in various catalytic processes.

The discovery of 1,3-Bis(diphenylphosphino)propane dates back to the mid-20th century when researchers were exploring the synthesis and properties of phosphine ligands. The development of dppp was part of a broader effort to create ligands that could form stable complexes with transition metals, which are essential in catalysis. The synthesis of dppp involves the reaction of 1,3-dibromopropane with two equivalents of diphenylphosphine, typically in the presence of a base to facilitate the substitution reaction. The resulting product, dppp, is a white crystalline solid that is soluble in many organic solvents, making it easy to handle and use in various chemical reactions.

One of the most important applications of dppp is in the field of palladium-catalyzed cross-coupling reactions, such as the Heck, Suzuki-Miyaura, and Stille reactions. In these reactions, dppp acts as a ligand that coordinates to the palladium center, stabilizing the metal and enhancing its catalytic activity. The chelating nature of dppp, with its two phosphine groups, allows it to form a stable five-membered ring with the palladium center, which is crucial for the catalytic cycle. The use of dppp in these reactions has enabled the efficient formation of carbon-carbon and carbon-heteroatom bonds, which are fundamental steps in the synthesis of a wide range of organic molecules, including pharmaceuticals, agrochemicals, and materials.

In addition to its role in cross-coupling reactions, dppp has been employed in hydrogenation and hydroformylation reactions. In hydrogenation, dppp is used as a ligand in catalysts that promote the addition of hydrogen to unsaturated substrates, such as alkenes and alkynes, converting them into saturated products. This reaction is of great industrial importance in the production of fine chemicals and pharmaceuticals. In hydroformylation, dppp is part of the catalytic system that adds a formyl group to alkenes, producing aldehydes. This reaction is particularly valuable in the synthesis of aldehydes that serve as intermediates in the production of alcohols, acids, and other functionalized organic compounds.

Beyond catalysis, 1,3-Bis(diphenylphosphino)propane has been studied for its coordination chemistry with various metal centers. The ability of dppp to form stable complexes with metals such as ruthenium, rhodium, and platinum has led to its use in the study of metal-ligand interactions and the development of new metal-based materials. These complexes are often characterized by their interesting electronic and structural properties, which can be fine-tuned by varying the metal and the ancillary ligands. This versatility has made dppp an important ligand in the design of metal complexes for applications in materials science, including the development of conductive polymers, catalysts for polymerization reactions, and photochemical systems.

The role of dppp in organometallic chemistry is further highlighted by its use in the stabilization of low-coordinate metal centers. The chelating nature of dppp helps to stabilize reactive metal species, allowing for the exploration of unusual oxidation states and coordination environments. These studies have provided valuable insights into the behavior of metals in catalysis and have led to the discovery of new catalytic processes and reaction mechanisms.

1,3-Bis(diphenylphosphino)propane continues to be a ligand of great interest in both academic research and industrial applications. Its ability to form stable metal complexes, combined with its effectiveness in catalysis, ensures its continued use in the development of new synthetic methods and the exploration of new chemical reactivity. As the field of catalysis evolves, dppp is likely to remain a key player in the design and implementation of catalytic systems that enable the efficient and sustainable production of a wide range of chemical products.

References

2023. Pincer Ru with a single stereogenic identity for highly efficient asymmetric transfer hydrogenation of ketones. Science China Chemistry, 66(5).
DOI: 10.1007/s11426-022-1535-7

2023. Development of a Synthetic Method for Tridentate Phosphine Ligands. Iron-Catalyzed C-H/C-H Coupling for Synthesis of Functional Small Molecules and Polymers, 3.
DOI: 10.1007/978-981-99-4121-6_3

1975. Phosphine-Nickel Complexes as Catalysts for Cross-Coupling Reaction of Grignard Reagents with Vinylic, Aromatic and Heteroaromatic Halides. Organotransition-Metal Chemistry, 19.
DOI: 10.1007/978-1-4684-2142-2_19