Bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate
[CAS# 99326-34-8]

Identification

• Classification: Organic raw materials >> Organometallic compound >> Organic rhodium
• Name: Bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate
• Synonyms: (5Z)-cycloocta-1,5-diene;rhodium;trifluoromethanesulfonate
• Molecular Formula: C₁₇H₂₄F₃O₃RhS
• Molecular Weight: 468.33
• CAS Registry Number: 99326-34-8
• EC Number: 624-823-5
• SMILES: C1C=CCC/C=C\C1.C1C=CCC/C=C\C1.C(S(=O)(=O)[O-])(F)(F)F.[Rh]

Properties

• Melting point: 159 ºC (dec.)
• Water solubility: insoluble

Safety Data

• Hazard Symbols: GHS07 Warning
• Hazard Statements: H302+H312+H332-H302-H312-H315-H319-H332-H335
• Precautionary Statements: P261-P264-P264+P265-P270-P271-P280-P301+P317-P302+P352-P304+P340-P305+P351+P338-P317-P319-P321-P330-P332+P317-P337+P317-P362+P364-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
Acute toxicity	Acute Tox.	4	H312
Acute toxicity	Acute Tox.	4	H302
Acute toxicity	Acute Tox.	4	H332

Discovory and Applicatios

Bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate is an organometallic complex with the formula Rh(C₈H₁₂)₂(CF₃SO₃). It consists of a rhodium(I) center coordinated by two 1,5-cyclooctadiene (COD) ligands and paired with a trifluoromethanesulfonate (triflate, CF₃SO₃⁻) counterion. This compound is a well-defined rhodium(I) complex widely used as a precursor or catalyst in homogeneous catalysis.

The complex is typically synthesized by reacting rhodium(I) chloride dimer with silver triflate in the presence of excess 1,5-cyclooctadiene ligands. The silver chloride precipitates out, leaving bis(1,5-cyclooctadiene)rhodium(I) triflate in solution. This method produces a soluble rhodium complex with labile triflate counterions that can be easily displaced or participate in catalytic cycles.

Bis(1,5-cyclooctadiene)rhodium(I) triflate is used extensively in organometallic chemistry and catalysis due to its stability, solubility, and ability to facilitate a variety of bond-forming reactions. The rhodium center, stabilized by the COD ligands, can coordinate to unsaturated substrates and activate them toward addition or insertion reactions. The triflate counterion is non-coordinating, which enhances the catalyst’s reactivity by leaving coordination sites open on the metal.

A major application of this complex is in the catalytic hydrogenation of alkenes and dienes, where it provides an alternative to traditional rhodium catalysts such as Wilkinson’s catalyst. It also serves as a catalyst precursor in hydroformylation reactions, hydroacylation, and carbon–carbon coupling processes including hydroboration, hydrosilylation, and cross-coupling reactions.

In homogeneous catalysis, the lability of the COD ligands allows them to be displaced by substrates, enabling the formation of reactive rhodium complexes that promote selective transformations under mild conditions. The triflate anion’s weak coordinating ability helps maintain the catalytic cycle efficiency by not strongly binding to the metal center.

Characterization of bis(1,5-cyclooctadiene)rhodium(I) triflate is typically done using nuclear magnetic resonance (NMR) spectroscopy, where signals for the COD ligands provide information about the ligand environment and coordination geometry. Infrared (IR) spectroscopy can identify triflate counterion vibrations. Elemental analysis and mass spectrometry confirm the complex’s composition and purity.

Handling of the complex requires standard precautions for air-sensitive organometallic compounds. It is usually stored under an inert atmosphere such as nitrogen or argon, in a dry, cool environment to prevent decomposition. It is soluble in common organic solvents like dichloromethane, tetrahydrofuran, and toluene, which facilitates its use in solution-phase catalytic reactions.

In summary, bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate is a versatile rhodium(I) complex used as a catalyst precursor in various homogeneous catalytic processes. Its combination of reactive rhodium center, labile COD ligands, and non-coordinating triflate anion enables efficient catalysis in organic synthesis, particularly in hydrogenation and carbon–carbon bond formation reactions. This compound plays a significant role in advancing organometallic catalysis and synthetic methodology.