dc.contributor.author | BAKER, ROBERT | en |
dc.date.accessioned | 2014-06-03T13:28:27Z | |
dc.date.available | 2014-06-03T13:28:27Z | |
dc.date.issued | 2006 | en |
dc.date.submitted | 2006 | en |
dc.identifier.citation | R.J. Baker, C. Jones, D.P. Mills, D.M. Murphy E. Hey-Hawkins and R. Wolf,, The reactivity of Gallium-(I), -(II) and -(III) heterocycles towards group 15 substrates: Attempts to prepare gallium-terminal pnictinidene complexes., Dalton Trans, 2006, 67, 72 | en |
dc.identifier.other | Y | en |
dc.identifier.uri | http://hdl.handle.net/2262/69580 | |
dc.description | PUBLISHED | en |
dc.description.abstract | The reactivity of a series of Ga(I), Ga(II) and Ga(III) heterocyclic compounds towards a number of Group 15 substrates has been investigated with a view to prepare examples of gallium–terminal pnictinidene complexes. Although no examples of such complexes were isolated, a number of novel complexes have been prepared. The reactions of the gallium(I) N-heterocyclic carbene analogue, [K(tmeda)][:Ga{[N(Ar)C(H)]2}] (Ar = 2,6-diisopropylphenyl) with cyclo-(PPh)5 and PhN[double bond, length as m-dash]NPh led to the unusual anionic spirocyclic complexes, [{κ2P,P′-(PhP)4}Ga{[N(Ar)C(H)]2}]− and [{κ2N,C-PhNN(H)(C6H4)}Ga{[N(Ar)C(H)]2}]−, via formal reductions of the Group 15 substrate. The reaction of the digallane(4), [Ga{[N(Ar)C(H)]2}]2, with (Me3Si)N3 afforded the paramagnetic, dimeric imido–gallane complex, [{[N(Ar)C(H)˙]2}Ga{μ-N(SiMe3)}]2, via a Ga–Ga bond insertion process. In addition, the new gallium(III) phosphide, [GaI{P(H)Mes*}{[N(Ar)C(H)]2˙}], Mes* = C6H2But3-2,4,6; was prepared and treated with diazabicycloundecane (DBU) to give [Ga(DBU){P(H)Mes*}{[N(Ar)C(H)]2}], presumably via a gallium–terminal phosphinidene intermediate, [Ga{[double bond, length as m-dash]PMes*}{[N(Ar)C(H)]2˙}]. The possible mechanisms of all reactions are discussed, all new complexes have been crystallographically characterised and all paramagnetic complexes have been studied by ENDOR and/or EPR spectroscopy. | en |
dc.format.extent | 67 | en |
dc.format.extent | 72 | en |
dc.language.iso | en | en |
dc.relation.ispartofseries | Dalton Trans | en |
dc.rights | Y | en |
dc.title | The reactivity of Gallium-(I), -(II) and -(III) heterocycles towards group 15 substrates: Attempts to prepare gallium-terminal pnictinidene complexes. | 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 | 57429 | en |
dc.identifier.doi | http://dx.doi.org/10.1039/b511451a | en |
dc.rights.ecaccessrights | openAccess | |