dc.contributor.author | BAKER, ROBERT | en |
dc.date.accessioned | 2014-06-03T13:32:41Z | |
dc.date.available | 2014-06-03T13:32:41Z | |
dc.date.issued | 2006 | en |
dc.date.submitted | 2006 | en |
dc.identifier.citation | S. Aldridge, R.J. Baker, N.D. Coombs, C. Jones, R.P. Rose, A. Rossin and D.J. Willock,, Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound., Dalton Trans.,, 2006, 3313, 3320 | en |
dc.identifier.other | Y | en |
dc.identifier.uri | http://hdl.handle.net/2262/69581 | |
dc.description | PUBLISHED | en |
dc.description.abstract | The reactivity of several transition metal half sandwich complexes towards an anionic gallium(I) heterocyclic complex, [K(tmeda)][Ga{[N(Ar)C(H)]2}] (Ar = C6H3Pri2-2,6), has been investigated. This has led to the anionic half sandwich complexes, [K(tmeda)][(C5H4R)M(CO)n[Ga{[N(Ar)C(H)]2}]] (M = V, R = H, n = 3; M = Mn, R = Me, n = 2; M = Co, R = H, n = 1), which crystallographic studies show to form dimers (M = Mn and Co) or a polymer (M = V) through bridging potassium cations. The metal–gallium bond lengths in all complexes are very short which, combined with some spectroscopic evidence, is suggestive of M–Ga π-bonding. Density functional theory studies of models of all complexes indicate that the level of back-bonding in these complexes is, however, minimal and of a similar order to that seen in analogous complexes incorporating neutral N-heterocyclic carbene ligands. Reactions of the metallocenes, [M(C5H4Me)2] (M = V or Cr), with the digallane(4), [Ga{[N(Ar)C(H)]2}]2, have afforded the neutral complexes, [M(C5H4Me)2[Ga{[N(Ar)C(H)]2}]], which are thought to be formed via an initial oxidative insertion of the transition metal centre into the Ga–Ga bond of the digallane. X-Ray crystallography shows the complexes to be monomeric. One (M = V) reacts with one equivalent of [K(tmeda)][Ga{[N(Ar)C(H)]2}] to give the crystallographically characterised, anionic bis(gallyl)-complex, [K(tmeda)][V(C5H4Me)2[Ga{[N(Ar)C(H)]2}]2]. For comparison, the reaction of [K(tmeda)][Ga{[N(Ar)C(H)]2}] with [Mn{CH(SiMe3)2}2] was carried out and gave the monomeric, anionic complex, [K(tmeda)][Mn{CH(SiMe3)2}2[Ga{[N(Ar)C(H)]2}]]. | en |
dc.format.extent | 3313 | en |
dc.format.extent | 3320 | en |
dc.language.iso | en | en |
dc.relation.ispartofseries | Dalton Trans., | en |
dc.rights | Y | en |
dc.subject | Chemistry | en |
dc.title | Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound. | en |
dc.type | Journal Article | en |
dc.type.supercollection | scholarly_publications | en |
dc.type.supercollection | refereed_publications | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/bakerrj | en |
dc.identifier.rssinternalid | 57430 | en |
dc.identifier.doi | http://dx.doi.org/10.1039/b604640a | en |
dc.rights.ecaccessrights | openAccess | |