Jump to main content
Jump to site search

Issue 27, 2006
Previous Article Next Article

Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound

Author affiliations

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}]].

Graphical abstract: Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound

Back to tab navigation

Supplementary files

Publication details

The article was received on 30 Mar 2006, accepted on 08 May 2006 and first published on 17 May 2006


Article type: Paper
DOI: 10.1039/B604640A
Dalton Trans., 2006, 3313-3320

  •   Request permissions

    Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound

    S. Aldridge, R. J. Baker, N. D. Coombs, C. Jones, R. P. Rose, A. Rossin and D. J. Willock, Dalton Trans., 2006, 3313
    DOI: 10.1039/B604640A

Search articles by author

Spotlight

Advertisements