Exploring novel M...C-C agostic interactions
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
Intermolecular and intramolecular interactions can have a significant effect on the properties of a particular compound, for example, in relation to its stability or reactivity. Understanding how an interaction occurs, its relative strength and how it can be altered is extremely important in fundamental structure and bonding terms. While there is a wealth of information available on some of the more common interactions, such as hydrogen bonding, this is not true for all types of interaction. Agostic transition metal...C-C interactions involve the donation of electron density from the carbon-carbon bond to the metal centre, this type of interaction is directly relevant to C-C activation, however, they are extremely rare and not well characterized for any technique.We propose to employ an integrated approach combining synthesis, NMR mapping and theoretical techniques with experimental charge density experiments in order to characterise and tune late transition metal...C-C agostic interactions. Importantly the study incorporates charge density studies which will, for the first time, allow the electronic structure of the interaction to be probed. The results of the study will provide synthetic routes, kinetic and thermodynamic data and experimental visualisation of such agostic interactions. This information will be of fundamental significance to the international chemical community, and will undoubtably be utilized in areas involving C-C activation, such as, novel organic synthesis and industrial applications, such as, petroleum cracking using heterogeneous catalysis.
Organisations
People |
ORCID iD |
Andrew Weller (Principal Investigator) |
Publications
Chaplin A
(2011)
[Rh{NC 5 H 3 -2,6-(CH 2 P t Bu 2 ) 2 }(PCy 3 )][BAr F 4 ]: A Latent Low-Coordinate Rhodium(I) PNP Pincer Compound
in Organometallics
Chaplin AB
(2009)
Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate.
in Chemical communications (Cambridge, England)
Chaplin AB
(2009)
Alkyl dehydrogenation in a Rh(I) complex via an isolated agostic intermediate.
in Chemical communications (Cambridge, England)
Chaplin AB
(2010)
Amine- and dimeric amino-borane complexes of the {Rh(P(i)Pr3)2}+ fragment and their relevance to the transition-metal-mediated dehydrocoupling of amine-boranes.
in Inorganic chemistry
Chaplin AB
(2010)
B-H activation at a rhodium(I) center: isolation of a bimetallic complex relevant to the transition-metal-catalyzed dehydrocoupling of amine-boranes.
in Angewandte Chemie (International ed. in English)
Chaplin AB
(2011)
C-C activation in the solid state in an organometallic s-complex.
in Journal of the American Chemical Society
Chaplin A
(2010)
C-C Bond Activation of a Cyclopropyl Phosphine: Isolation and Reactivity of a Tetrameric Rhodacyclobutane
in Organometallics
Sparkes HA
(2011)
Experimental charge density study into C-C s-interactions in a Binor-S rhodium complex.
in Dalton transactions (Cambridge, England : 2003)
Douglas TM
(2009)
Monomeric and oligomeric amine-borane sigma-complexes of rhodium. intermediates in the catalytic dehydrogenation of amine-boranes.
in Journal of the American Chemical Society