The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

Eliasson, Sondre H. Hopen; Chatterjee, Anamitra; Occhipinti, Giovanni; Jensen, Vidar R.

doi:10.3390/inorganics5040087

Cited by 10 publications

(26 citation statements)

References 59 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Initially, reaction (1) was achieved on fatty acid with the aid of an anhydride additive (like acetic anhydride) and Pdor Rh-based complexes with good LAO selectivity: 14,16 R-CH2-CH2-COOH + (CH3CO)2O  R-CH=CH2 + CO + 2CH3COOH (3) More recently, it was shown that (3) can be performed effectively with metallic Pt or Pd on C preserving the high selectivity toward LAO. 17,18 The mechanism of such dehydration-decarbonylation reactions is discussed in detail by Eliasson et al 19 The research on LAO formation from fatty acids involved also the adoption of pre-formed Pdcomplexes which reduce the amount of triphenylphosphine (TPP) used as reaction solvent, 20 and a study on the effect of different phosphine ligand structures on the selectivity toward LAO or the conversion of fatty acids to LO/LAO with Pd complexes. [21][22][23] The research also moved toward the study of more economical and wide available catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…Once the anhydride is formed there is the interaction with the metal catalyst, with oxidative addition of the metal, the decarbonylation step and the alkene formation and release. 19 In literature the complex bis(triphenylphosphine)nickel(II) dichloride (i.e. (Ph3P)2NiCl2) was reported as an effective decarbonylation reagent of certain cycloaliphatic anhydrides.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Linear Olefins From Fatty Acids: A Comparison of Nickel(i) and Rhodium(i) Catalysts in Liquid Triphenylphosphine

Cataldo¹

2019

ECB

View full text Add to dashboard Cite

Linear α-olefins (LAO) with good selectivity toward linear olefins (LO) can be synthesized from widely available fatty acids (lauric, decanoic, miristic, palmitic and stearic acids) in high yield using a Ni(II) complex: Ni(Ph3P)2Cl2 in liquid triphenylphosphine (TPP). It is shown spectrophotometrically, in liquid triarylphosphine that Ni(Ph3P)2Cl2 assumes an octahedral coordination geometry which is believed to be the active species in the dehydration-decarbonylation reaction of fatty acids. For comparison also the Wilkinson's catalyst, i.e., the Rh(I) complex Rh(Ph3P)3Cl was also studied as a fatty acid decarbonylation catalyst in liquid TPP. The Wilkinson's catalyst gives an extremely smooth >95% selectivity toward LAO. Thus, when high LAO selectivity is requested, Rh(Ph3P)3Cl is the catalyst of choice. On the other hand, when economic LO/LAO mixtures are requested in high yields, for instance as in the case of hydroformylation feedstocks, then Ni(Ph3P)2Cl2 is the recommended catalyst. The LO/LAO products were determined with GC-MS and the LAO selectivity was also determined with Raman spectroscopy.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Linear Olefins From Fatty Acids: A Comparison of Nickel(i) and Rhodium(i) Catalysts in Liquid Triphenylphosphine

Cataldo¹

2019

ECB

View full text Add to dashboard Cite

show abstract

“…Only during the work with this thesis, have the first computational studies of the reaction arrived. 66,74,[81][82][83][84] This lack of mechanistic information has stifled the understanding of different factors of the reaction and rational design of better catalysts, and was partly the motivation for synthesizing the molecular well-defined precatalyst A1, Pd(cinnamyl)Cl(DPEphos). 85 While previous catalysts for decarbonylative dehydration have been formed in situ, this catalytic system was able to transform fatty acids to α-olefin at relatively mild conditions (110°C) and, importantly, without excess of phosphine.…”

Section: Introductionmentioning

confidence: 99%

Selective production of linear α-olefins via catalytic deoxygenation of fatty acids and derivatives

Chatterjee

Eliasson

Jensen

2018

Catal. Sci. Technol.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Eliasson, Chatterjee, Occhipinti and Jensen published a comprehensive computational study on the mechanism of the Rh-mediated decarbonylative dehydration of fatty acids to provide linear terminal alkenes (LAO) and carboxylic acid, with anhydride as the co-reagent [29]. Furthermore, the authors investigated the mechanism of Pd-systems for the same reaction in order to find similarities and differences between both catalyst types, to draw conclusions regarding the relative rates and to provide avenues for catalyst optimization.…”

mentioning

confidence: 99%

“…Furthermore, the authors investigated the mechanism of Pd-systems for the same reaction in order to find similarities and differences between both catalyst types, to draw conclusions regarding the relative rates and to provide avenues for catalyst optimization. Linear terminal alkenes or linear alpha olefins are key commodity chemicals and petrochemical intermediates that are e.g., used in the large-scale technical synthesis of oxo alcohols to give detergents and plasticizers [29], using e.g., the hydroformylation reaction [2].…”

mentioning

confidence: 99%

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

2018

View full text Add to dashboard Cite

Man-made homogeneous catalysis with the aid of transition metal compounds looks back on a long history of almost one hundred years. Still, more detailed insight into the underlying mechanisms is warranted. The knowledge of how transition metals with their specific/characteristic properties, such as oxidations states, redox chemistry, spin states, kinetics, and coordination preference will contribute to these processes paving the way to optimize existing processes, and to finding new exciting organic, inorganic, and organometallic transformations and to broaden the substrate scope through catalyst design. This special issue collects very recent mechanistic insight from experimental, theoretical, and mixed experimental-theoretical approaches.At the very end of the 19th century, Alfred Werner established the basis of our modern understanding of (transition) metal complexes [1]. When Otto Roelen discovered and developed the hydroformylation reaction (or Oxo Process) in the late 1930s, probably the first milestone in homogeneous catalysis, serendipity played an important role [2,3]. A deeper understanding of the specific interactions of ligands and metals came only later with the development of binding concepts such as the ligand field theory and the molecular orbital theory, e.g., the Dewar-Chatt-Duncanson model, which was developed in the 1950s for the binding of olefins to transition metals [4]. Originally dedicated to the binding situation of the complex anion of the Zeise salt [PtCl 3 (ethene)] -, it soon became clear that homogeneously metal-catalyzed transformations of olefins can be described and understood using this concept [4][5][6][7]. Probably the most prominent examples of such olefin complexes are the Pd derivatives of the Zeise anion [PdCl 3 (olefin)] − , which were the pivotal species of today's technically most important organocatalytic process, the Wacker Process (or Wacker Oxidation), which was developed starting in the 1950s [7][8][9][10].About 80 years after Roelen's hydroformylation, on a list of recently identified "holy grails" in chemistry "perfect catalysis" is prominently in the top ten [11] and homogeneous transition metal catalysis provides the basis for many desired transformations, e.g., in C-H aminations, in site-selective bond activations, for the functionalization of alkanes or in oxidative couplings yielding complex target molecules. Even since the rise of "metal-free" organo-catalysis at the beginning of our millennium and its enormous impact on organic transformations, the meanwhile established "classical" (transition) metal mediated applications reside as solid pillars in the toolbox for chemical synthesis [12][13][14]. Recent Nobel Prizes in chemistry, i.e., 2010 to Richard F. Heck, Ei-ichi Negishi and Akira Suzuki, 2005 to Yves Chauvin, Robert H. Grubbs and Richard R. Schrock, as well as 2001 to William S. Knowles, Ryoji Noyori and K. Barry Sharpless [14,15] clearly highlight homogeneous transition metal catalysis as an outstanding discipline, crucial for various are...

show abstract

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

Cited by 10 publications

References 59 publications

Synthesis of Linear Olefins From Fatty Acids: A Comparison of Nickel(i) and Rhodium(i) Catalysts in Liquid Triphenylphosphine

Synthesis of Linear Olefins From Fatty Acids: A Comparison of Nickel(i) and Rhodium(i) Catalysts in Liquid Triphenylphosphine

Selective production of linear α-olefins via catalytic deoxygenation of fatty acids and derivatives

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

Contact Info

Product

Resources

About