4308-14-9Relevant articles and documents
Convergent Synthesis of a Metal-Organic Framework Supported Olefin Metathesis Catalyst
Yuan, Jian,Fracaroli, Alejandro M.,Klemperer, Walter G.
, p. 2149 - 2155 (2016/07/07)
Synthesis of a metal-organic framework (MOF)-supported olefin metathesis catalyst has been accomplished for the first time following a new, convergent approach where an aldehyde-functionalized derivative of Hoveyda's recently reported ruthenium catecholate olefin metathesis catalyst is condensed with an amine-functionalized IRMOF-74-III. The resulting material, denoted MOF-Ru, has well-defined, catalytically active ruthenium centers confined within channels having a ca. 20 ? diameter. MOF-Ru is a recyclable, single-site catalyst for self-cross-metathesis and ring-closing metathesis of terminal olefins. Comparison of this heterogeneous catalyst with a homogeneous analogue shows different responses to substrate size and shape suggestive of confinement effects. The MOF-Ru catalyst also displays greater resistance to double-bond migration that can be attributed to greater catalyst stability. For the preparation of well-defined, single-site heterogeneous catalysts where catalyst purity is essential, the convergent approach employed here, where the catalytic center is prepared ex situ and covalently linked to an intact MOF, offers an attractive alternative to in situ catalyst preparation as currently practiced in MOF chemistry.
Accelerating influence of the gem-difluoromethylene group in a ring-closing olefin metathesis reaction. A Thorpe-Ingold effect?
Urbina-Blanco, Cesar A.,Skibinski, Maciej,O'Hagan, David,Nolan, Steven P.
supporting information, p. 7201 - 7203 (2013/08/15)
The gem-difluoromethylene (CF2) group significantly accelerates ring-closing metathesis of 1,8-nonadienes relative to the methylene (CH 2) group demonstrating similar rate accelerations to that observed for the classic Thorpe-Ingold substituents, diester malonates and ketals.
