1,3-Bis(dicyclohexylphosphino)propane
[CAS# 103099-52-1]

Identification

• Classification: Organic raw materials >> Organic phosphine compound
• Name: 1,3-Bis(dicyclohexylphosphino)propane
• Synonyms: dicyclohexyl(3-dicyclohexylphosphanylpropyl)phosphane
• Molecular Formula: C₂₇H₅₀P₂
• Molecular Weight: 436.63
• CAS Registry Number: 103099-52-1
• EC Number: 889-568-6
• SMILES: C1CCC(CC1)P(CCCP(C2CCCCC2)C3CCCCC3)C4CCCCC4

Properties

• Density: 1.05
• Boiling point: 350 ºC
• Refractive index: 1.554
• Flash point: 113 ºC

Safety Data

• Hazard Symbols: GHS07 Warning
• Hazard Statements: H315-H319-H335
• Precautionary Statements: P261-P264-P264+P265-P271-P280-P302+P352-P304+P340-P305+P351+P338-P319-P321-P332+P317-P337+P317-P362+P364-P403+P233-P405-P501

Discovory and Applicatios

1,3-Bis(dicyclohexylphosphino)propane, commonly abbreviated as dcypp, is a bidentate ligand that has garnered significant interest in the field of organometallic chemistry and catalysis. The discovery of this compound can be traced to the broader efforts in the mid-20th century to develop novel phosphine ligands that could enhance the reactivity and selectivity of metal catalysts. Its structure, featuring two dicyclohexylphosphino groups linked by a three-carbon propane chain, offers both steric bulk and flexibility, making it particularly valuable in catalysis.

The synthesis of 1,3-bis(dicyclohexylphosphino)propane involves the reaction of dicyclohexylphosphine with 1,3-dihalopropane, typically under basic conditions. The resulting compound is a versatile ligand that can coordinate to various transition metals, forming stable complexes. These metal-ligand complexes have been found to exhibit unique properties, especially in catalytic processes. The steric hindrance provided by the bulky dicyclohexyl groups, coupled with the flexibility of the propane linker, allows for fine-tuning of the electronic environment around the metal center, which can significantly influence catalytic activity.

One of the most notable applications of 1,3-bis(dicyclohexylphosphino)propane is in homogeneous catalysis, particularly in hydrogenation reactions. When coordinated with transition metals such as rhodium or ruthenium, the resulting complexes have demonstrated high efficiency and selectivity in the hydrogenation of alkenes, alkynes, and carbonyl compounds. The ability of dcypp to promote these reactions under mild conditions has made it an attractive ligand in both academic research and industrial applications. For example, its use in the hydrogenation of functionalized alkenes has provided a valuable tool for the synthesis of fine chemicals and pharmaceuticals.

In addition to hydrogenation, 1,3-bis(dicyclohexylphosphino)propane has found utility in cross-coupling reactions, such as the Heck and Suzuki reactions. These reactions are fundamental in the formation of carbon-carbon bonds, which are crucial in the synthesis of complex organic molecules. The bulky nature of dcypp helps to stabilize the metal center during the catalytic cycle, thereby enhancing the turnover numbers and prolonging the catalyst's life. This has made dcypp-containing catalysts highly sought after in synthetic organic chemistry, where the formation of specific carbon-carbon bonds with high precision is essential.

The versatility of 1,3-bis(dicyclohexylphosphino)propane is not limited to its role as a ligand in catalysis. It has also been explored for its potential in material science, particularly in the development of metal-organic frameworks (MOFs). The rigid yet flexible nature of the dcypp ligand allows for the construction of robust MOFs with interesting structural and electronic properties. These materials have potential applications in gas storage, separation, and catalysis. The ability to incorporate dcypp into MOFs opens up new avenues for designing materials with tailored properties for specific applications.

Furthermore, the study of 1,3-bis(dicyclohexylphosphino)propane and its metal complexes has provided valuable insights into the fundamental aspects of coordination chemistry. Understanding how the steric and electronic properties of dcypp influence metal-ligand interactions has helped chemists design more efficient and selective catalysts. This has implications not only in catalysis but also in the broader field of organometallic chemistry, where the development of new ligands is crucial for advancing the field.

In conclusion, 1,3-bis(dicyclohexylphosphino)propane is a ligand of considerable importance in modern chemistry. Its discovery and subsequent applications in catalysis, material science, and coordination chemistry have underscored its versatility and utility. The continued exploration of dcypp and its derivatives promises to yield further advancements in these fields, contributing to the development of more efficient and sustainable chemical processes.

References

2016. Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2. Topics in Current Chemistry (Cham), 374(4).
DOI: 10.1007/s41061-016-0045-z

2020. Cobalt-Catalyzed Decarboxylative Methylation and Ethylation of Aliphatic N-(Acyloxy)phthalimides with Organoaluminum Reagents. Synlett, 31(10).
DOI: 10.1055/s-0040-1707946