Dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium (II)
[CAS# 132071-87-5]

Identification

• Classification: Organic raw materials >> Organic phosphine compound
• Name: Dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium (II)
• Synonyms: (S)-BINAP dichlororuthenium complex
• Molecular Formula: C₄₄H₃₂Cl₂P₂Ru
• Molecular Weight: 794.65
• CAS Registry Number: 132071-87-5
• EC Number: 623-973-9
• SMILES: C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=C(C4=CC=CC=C4C=C3)C5=C(C=CC6=CC=CC=C65)P(C7=CC=CC=C7)C8=CC=CC=C8.Cl[Ru]Cl

Properties

• Melting point: >300 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

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Specific target organ toxicity - single exposure	STOT SE	3	H335
Eye irritation	Eye Irrit.	2	H319
Skin irritation	Skin Irrit.	2	H315
Skin sensitization	Skin Sens.	1	H317
Chronic hazardous to the aquatic environment	Aquatic Chronic	3	H412

Discovory and Applicatios

Dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium(II), commonly referred to as (S)-BINAP-ruthenium(II) dichloride, is a chiral organoruthenium complex that plays a significant role in asymmetric catalysis. This compound consists of a ruthenium(II) center coordinated to the (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl ligand, which imparts chirality to the complex. The development and use of this complex has been a major advancement in the field of synthetic chemistry, particularly for the selective synthesis of chiral molecules.

The (S)-BINAP ligand, the core chiral component of this catalyst, was first introduced in the 1980s as a highly effective chiral ligand for transition metal catalysis. The use of (S)-BINAP in coordination with various transition metals, including ruthenium, was recognized for its ability to induce high levels of stereoselectivity in catalytic reactions. The unique properties of the (S)-BINAP ligand, such as its rigid biphenyl backbone and the spatial arrangement of its bulky diphenylphosphine groups, provide a highly effective means for controlling the stereochemistry of reactions, making it an essential tool in asymmetric synthesis.

The coordination of ruthenium(II) to the (S)-BINAP ligand enables the catalyst to facilitate a variety of important asymmetric transformations. One of the most notable applications of dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium(II) is in asymmetric hydrogenation reactions. In this process, the catalyst selectively hydrogenates alkenes or imines to form chiral products with high enantiomeric excess. This ability to catalyze asymmetric hydrogenations is critical for the production of chiral intermediates used in the pharmaceutical industry, where specific enantiomers often exhibit vastly different biological activities.

Another key application of (S)-BINAP-ruthenium(II) dichloride is in the asymmetric transfer hydrogenation of carbonyl compounds, which is a widely used method for producing chiral alcohols. The catalyst facilitates the transfer of hydrogen from a donor to a carbonyl group, generating an alcohol with high stereoselectivity. This reaction is particularly valuable in synthetic organic chemistry, where the ability to selectively produce one enantiomer over another is essential in the synthesis of complex molecules.

The complex also plays an important role in various other transformations, such as the asymmetric addition of nucleophiles to electrophiles, in which the ruthenium center mediates the transfer of a nucleophile to a substrate while controlling the stereochemistry of the product. Such reactions are widely utilized in the synthesis of fine chemicals, agrochemicals, and materials.

The stability and reactivity of dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium(II) make it an ideal candidate for catalytic processes that require high selectivity and efficiency. The (S)-BINAP ligand ensures that the ruthenium center is properly coordinated to the substrate, facilitating the formation of chiral intermediates with high enantioselectivity. In addition, the use of ruthenium as the central metal in the catalyst allows for mild reaction conditions and high turnover rates, further enhancing its utility in industrial-scale processes.

In summary, dichloro[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium(II) is a crucial catalyst in modern asymmetric synthesis. Its development marked a significant step forward in the field of chiral catalysis, providing a reliable means of producing chiral compounds with high selectivity. Its applications in asymmetric hydrogenation, transfer hydrogenation, and nucleophilic addition reactions have made it an invaluable tool in both research and industrial chemistry, particularly in the pharmaceutical and fine chemicals industries. The combination of the (S)-BINAP ligand’s steric properties and the versatile reactivity of the ruthenium center continues to make this catalyst a mainstay in synthetic chemistry.

References

1991. [2,2'-Dimethyl-6,6'-bis(diphenylphosphino)biphenyl](triphenylphosphine)-dichlororuthenium(II): an enantioselective catalyst for the hydrogenation of diketones. Journal of the Chemical Society, Chemical Communications, (24).
DOI: 10.1039/C39910001675

2022. Aggregation-induced polarization (AIP) of derivatives of BINOL and BINAP. RSC Advances, 12(46).
DOI: 10.1039/D2RA05597J