TY - JOUR
T1 - Synthesis and characterisation of anionic and neutral gallium(I) N-heterocyclic carbene analogues
AU - Dange, Deepak Sadashiv
AU - Choong, Sam Lim
AU - Schenk, Christian
AU - Stasch, Andreas
AU - Jones, Cameron
PY - 2012
Y1 - 2012
N2 - A high yield synthesis of a new, extremely bulky anionic gallium(I) N-heterocyclic carbene analogue, [(DAB*)Ga:]- (DAB* = N(Ar*)C(H) 2, Ar* = C6H2 C(H)Ph2 2Me-2,6,4) has been developed and four monomeric sodium complexes of the heterocycle have been crystallographically characterised. The gallium(I) heterocycle has been utilised in the preparations of the heteroleptic zinc and cadmium gallyl complexes, [(DAB*)GaMX(tmeda)] (M = Zn or Cd, X = Br or I), which were crystallographically characterised. In addition, [(DAB*)Ga:]- was oxidatively coupled to give the diamagnetic digallane(4), [(DAB*)GaGa(DAB*)]. The moderate yield synthesis of the six-membered gallium(I) heterocycle, [(ButMesNacnac)Ga:] (ButMesNacnac = [(MesNCBut)2CH]-, Mes = mesityl), is described, and the compound found to be a monomer in the solid state by an X-ray crystallographic analysis. A low yield by-product from this synthesis, [Ga5I4(ButMesNacnac)3], was also isolated and shown by X-ray crystallography to be a rare example of a compound bearing a group 13 metal-metal bonded chain stabilised by Beta-diketiminate ligands. A preliminary analysis of the bonding in the compound was carried out using DFT calculations.
AB - A high yield synthesis of a new, extremely bulky anionic gallium(I) N-heterocyclic carbene analogue, [(DAB*)Ga:]- (DAB* = N(Ar*)C(H) 2, Ar* = C6H2 C(H)Ph2 2Me-2,6,4) has been developed and four monomeric sodium complexes of the heterocycle have been crystallographically characterised. The gallium(I) heterocycle has been utilised in the preparations of the heteroleptic zinc and cadmium gallyl complexes, [(DAB*)GaMX(tmeda)] (M = Zn or Cd, X = Br or I), which were crystallographically characterised. In addition, [(DAB*)Ga:]- was oxidatively coupled to give the diamagnetic digallane(4), [(DAB*)GaGa(DAB*)]. The moderate yield synthesis of the six-membered gallium(I) heterocycle, [(ButMesNacnac)Ga:] (ButMesNacnac = [(MesNCBut)2CH]-, Mes = mesityl), is described, and the compound found to be a monomer in the solid state by an X-ray crystallographic analysis. A low yield by-product from this synthesis, [Ga5I4(ButMesNacnac)3], was also isolated and shown by X-ray crystallography to be a rare example of a compound bearing a group 13 metal-metal bonded chain stabilised by Beta-diketiminate ligands. A preliminary analysis of the bonding in the compound was carried out using DFT calculations.
UR - http://pubs.rsc.org.ezproxy.lib.monash.edu.au/en/content/articlepdf/2012/dt/c2dt30299c
U2 - 10.1039/c2dt30299c
DO - 10.1039/c2dt30299c
M3 - Article
SN - 1477-9226
VL - 41
SP - 9304
EP - 9315
JO - Dalton Transactions
JF - Dalton Transactions
IS - 31
ER -