Experimental and DFT investigation of the 1-octene metathesis reaction mechanism with the Grubbs 1 precatalyst

Jordaan, Margaritha; Helden, Pieter van; Sittert, Cornelia Gertina Catharina Elizabeth van; Vosloo, Hermanus C.M.

doi:10.1016/j.molcata.2006.03.022

Cited by 38 publications

(36 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 8 illustrates the change in the peak integration values of the individual carbene species as a function of time. The methylidene intermediate seems to follow a different pattern than what was reported for 1 [20] in which it seems the signal increases to a maximum with a gradual decrease without it being depleted in the 5 h the reaction proceeds. The benzylidene signal gradually decreases suggesting the conversion of the benzylidene to the heptylidene and methylidene; after 200 min all of 4a has been converted.…”

Section: Nmr Investigation: Metathesis With 4acontrasting

confidence: 65%

“…[20] As a result of double-bond isomerisation occurring during the metathesis reaction secondary cross-metathesis between the various alkenes can take place yielding a range of C 2 -C 14 alkene products. Therefore three major groups of products can be identified, i.e., primary metathesis products (PMP), isomerisation products (IP) and secondary metathesis products (SMP).…”

Section: Metathesis Of 1-octene Using 4a Andmentioning

confidence: 99%

“…The individual species seems to follow a similar pattern as was reported for 1 in which it has been shown that the heptylidene is thermodynamically and kinetically favoured above the methylidene species. [20] The sharp decrease of the benzylidene signal suggests a fast conversion of the benzylidene to either the uncoordinated benzylidene intermediate (7-open) or the heptylidene and methylidene; after 50 min all of 7 has been converted. The simultaneous decomposition of the benzylidene to some other species cannot be ruled out.…”

Section: Nmr Investigation: Metathesis Withmentioning

confidence: 99%

See 2 more Smart Citations

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Jordaan¹,

Vosloo²

2007

Adv Synth Catal

View full text Add to dashboard Cite

The catalytic activity of ruthenium alkylidene complexes [RuCl(L), bearing a chelating pyridinyl-alcoholate ligand, was investigated for the metathesis of 1-octene in the absence of a solvent. Both systems were active for the metathesis of 1-octene yielding trans-7-tetradecene and ethene as the primary metathesis products. Although the activity of both systems increased with an increase in reaction temperature, the activity ofstarted to decrease at temperatures above 70 8C, with a simultaneous exponential increase in the secondary metathesis products due to double-bond isomerisation of the substrate. Although the initiation rates for these systems are slower compared to Grubbs 1 and Grubbs 2 for the metathesis of 1-octene at 60 8C, they have a higher activity and longer lifetime.

show abstract

Section: Nmr Investigation: Metathesis With 4acontrasting

confidence: 65%

Section: Metathesis Of 1-octene Using 4a Andmentioning

confidence: 99%

Section: Nmr Investigation: Metathesis Withmentioning

confidence: 99%

See 1 more Smart Citation

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Jordaan¹,

Vosloo²

2007

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…Several other computational studies have also been done on the mechanism of Grubbs-type catalysts [44][45][46][47][48][49][50][51][52][53], but none focused primarily on the use of frontier orbitals and NBO as activity indicators. Whereas, Lord et al [54] and Suresh and Koga [55] investigated only the molecular orbital overlaps of the metallacyclobutane intermediate but made no mention of the initial orbital interaction of the catalyst with the alkene.…”

Section: Introductionmentioning

confidence: 99%

Towards a better understanding of alkene metathesis: elucidating the properties of the major metal carbene catalyst types

2015

View full text Add to dashboard Cite

The difference in activity of metal carbene catalysts has a major influence on the efficiency and application of these metal carbenes as metathesis catalysts. The focus of this research is to examine the properties of the major metal carbene catalyst types to understand the general activity trend. A comparative investigation of the foremost Fischer-, Tebbe-, Grubbs-, and Schrock-type metal carbenes was done using a qualitative structure-activity type computational method via principal component analysis. The effect of the change in metal atom as well as the change in ligands was specifically considered. Four Fischer-, a Tebbe-, five Grubbs-, and a Schrock-type carbene were investigated in this regard. Geometry optimizations of all species were done at the GGA/PBE/ DNP level with Materials Studio DMol 3 and subsequent single-point energy calculations were done with Gaussian at the PBEPBE level with the cc-pVQZ-type basis sets. Results showed that the descriptors extracted by the principal component analyses could successfully reproduce or match the generalized trend for metathesis activity, highlighting the importance of the frontier orbitals in the metathesis reaction. Graphical Abstract

show abstract

“…DMol 3 is a unique density functional theory quantum mechanical code that allows users to study problems in the chemical and pharmaceutical industry as well as in materials science with high accuracy and reliability. DMol 3 can simulate processes in gas phase [22,23], solvent [24,25], surface [26][27][28] and so on, which makes it well suited to research problems in chemistry, materials science, chemical engineering, and solid state physics.…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation on the reaction of adhesion unit dopa in mussel with electrolyzing seawater

Chen

Wang

Zhou

et al. 2009

Colloids and Surfaces B: Biointerfaces

View full text Add to dashboard Cite

Experimental and DFT investigation of the 1-octene metathesis reaction mechanism with the Grubbs 1 precatalyst

Cited by 38 publications

References 31 publications

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Towards a better understanding of alkene metathesis: elucidating the properties of the major metal carbene catalyst types

Theoretical investigation on the reaction of adhesion unit dopa in mussel with electrolyzing seawater

Contact Info

Product

Resources

About