Ruthenium CAAC Catalysts for Ethanolysis Activity

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Solution Overview

Problem

Current catalysts for ethenolysis reactions are not sufficiently active or selective for industrial-scale production of terminal olefins using ethylene gas, leading to high catalyst loadings and increased costs.

Innovation Solution

Development of ruthenium complexes with cyclic alkyl amino carbene (CAAC) ligands, such as C578 (Me, iPr) and C782, which exhibit high activity and selectivity in ethenolysis reactions, achieving turnover numbers (TONs) exceeding 100,000 and up to 330,000, enabling sustainable industrial-scale production.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If conventional catalysts are used for ethenolysis reactions, then the reaction can proceed, but high catalyst loadings are required resulting in increased costs and reduced productivity

Engineering Contradiction:
Improvecatalyst activityVSAvoidcatalyst loading
Core Design Contradiction:
ProductivityVSQuantity of substance

Solution Approach 1:

The patent modifies the ligand parameters of the ruthenium catalyst by introducing cyclic alkyl amino carbene (CAAC) ligands with specific structural features (ortho-substituted N-aryl groups). These parameter changes in the catalyst structure dramatically increase catalytic activity, reducing required catalyst loading from conventional high levels to as low as 10 ppm while maintaining high turnover numbers (TON > 100,000).

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite catalyst system combining ruthenium metal center with specifically designed CAAC ligands featuring cyclic alkyl amino carbene structures. This composite material approach, where the ligand and metal work synergistically, produces a catalyst with enhanced activity and stability, enabling industrial-scale ethenolysis with minimal catalyst loading.

Inventive Principle:
Principle #40Composite materials

2Manufacturing precision

If conventional catalysts are used for ethenolysis reactions, then the reaction can proceed, but selectivity for terminal olefins is insufficient leading to product mixture and purification challenges

Engineering Contradiction:
ImproveselectivityVSAvoidproduct purification
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent introduces local structural features (ortho-substituents on the N-aryl ring of the CAAC ligand) that create a specific steric and electronic environment at the catalytic site. This local modification of the catalyst structure enhances selectivity for terminal olefin production by controlling the orientation and reactivity of the substrate at the active site, minimizing formation of internal olefin byproducts.

Inventive Principle:
Principle #3Local quality

3Manufacturing precision

If high catalyst loadings are used to achieve good selectivity, then terminal olefin production improves, but production costs increase making the process economically unviable

Engineering Contradiction:
Improveterminal olefin selectivityVSAvoidproduction cost
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

By changing the chemical parameters of the catalyst (using CAAC ligands instead of conventional phosphine or NHC ligands), the patent achieves high selectivity at extremely low catalyst loadings (10 ppm). This parameter change transforms the cost structure by reducing the amount of expensive ruthenium metal required while maintaining high selectivity for terminal olefins.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

These ruthenium complexes significantly enhance the activity and selectivity of ethenolysis reactions, reducing catalyst loadings and lowering production costs, making the process more economically viable and environmentally friendly.

Implementation Method 1

contacting the at least one olefinic substrate with the at least one alpha olefin in the presence of a ruthenium complex bearing a cyclic alkyl amino carbene ligand under reaction conditions effective to allow a metathesis reaction to occur

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3904362A1Reactions in the presence of ruthenium complexes
Publication Date: 2021.11.03 CALIFORNIA INST OF TECH
  • EP3904362A1 patent drawingFigure 1
  • EP3904362A1 patent drawingFigure 2
  • EP3904362A1 patent drawingFigure 3a

AI summary

Described herein are compounds and methods for catalyzing metathesis reactions. The compounds described herein are ruthenium complexes bearing cyclic alkyl amino carbene (CAAC) ligands. The ruthenium complexes bearing cyclic alkyl amino carbene ligands may be used for catalyzing metathesis reactions, such as ethenolysis and alkenolysis reactions.