Multi N-Heterocyclic Carbene Complexes of Ruthenium for the Coordination and Reactivity of Small Molecules

Project: Research council

Project Details

Description

The utilisation of small molecules such as O2, H2 and N2 in chemical transformations relies on them being able to first coordinate to reactive transition metal complexes. We have recently reported (J. Am. Chem. Soc. 2009, 131, 9618; Chem. Eur. J. 2009, 15, 10912) a new ruthenium complex containing four N-heterocyclic carbene (NHC) ligands that shows selectivity in binding these gases as a function of the NHC substituents. We now wish to build upon these initial observations to see whether this Ru multi-NHC 'scaffold' can be used to incorporate the bound O2, H2 and N2 molecules into catalytic reactions (oxidation, hydrogenation etc) and, on the basis or additional preliminary results, whether we can induce more exotic types of molecules such as white phosphorus (P4) and ammonia boranes (R2HNBH3) to take part in both novel stoichiometric and catalytic transformations.Efforts will be directed at preparing new Ru(NHC)4 fragments that contain abnormally coordinated NHCs, afford reactive heteroatom hydride products and precursors to long sought after naked 16e RuL4 species for intermolecular C-H activation. We will build upon more preliminary results with a Ru(NHC)3 fragment in an effort to bring about catalytic H-X addition to alkenes. It is important to establish whether the rich chemistry of these multi-NHC complexes hinted at by our published work and preliminary data can be extended on from Ru to other transition metals, both in the same group (specifically Fe) and surrounding groups (Mo, W, Re).
StatusFinished
Effective start/end date4/10/103/04/14

Funding

  • Engineering and Physical Sciences Research Council

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  • Research Output

    Rh-FHF and Rh-F complexes containing small N-alkyl substituted six-membered ring N-heterocyclic carbenes

    Bramananthan, N., Carmona, M., Lowe, J. P., Mahon, M. F., Poulten, R. C. & Whittlesey, M. K., 28 Apr 2014, In : Organometallics. 33, 8, p. 1986-1995 10 p.

    Research output: Contribution to journalArticle

  • 20 Citations (Scopus)

    Synthesis and small molecule reactivity of trans-dihydride isomers of Ru(NHC)2(PPh3)2H2 (NHC = N-Heterocyclic Carbene)

    Davies, C. J. E., Lowe, J. P., Mahon, M. F., Poulten, R. C. & Whittlesey, M. K., 9 Sep 2013, In : Organometallics. 32, 17, p. 4927-4937 11 p.

    Research output: Contribution to journalArticle

  • 16 Citations (Scopus)

    Formation of cyclometallated N-heterocyclic carbene (NHC) complexes from L nRuCl 2 (L = Cyclooctadiene, PPh 3, DMSO) precursors

    Bramananthan, N., Mas-Marza, E., Fernandez, F. E., Ellul, C. E., Mahon, M. F. & Whittlesey, M. K., 2012, In : European Journal of Inorganic Chemistry. 2012, 13, p. 2213-2219 7 p.

    Research output: Contribution to journalArticle

  • 17 Citations (Scopus)