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摘要
New neutral and anionic fluoroaryl gold(I) complexes featuring terminal pyridine rings were prepared following different strategies. The homoleptic anionic compounds NBu4-[Au(C5F4N)(2)] (1) and NBN[Au(C(6)F(4)py)(2)] (2) were obtained by reacting [AuCl(tht)] (tht = tetrahydrotlilophene) with the organolithium derivatives of BrC5F4N and BrC(6)F(4)py, respectively. This route required the previous synthesis of the new fluorinated compound BrC(6)F(4)py, which was produced by a Stifle cross-coupling between (4-pyridyl)trimethylstannane and 1,4-dibromotetrafluorobenzene. The neutral phosphane compounds [Au(C6F4N)(PPh3)] (3) and [Au(C(6)F(4)py)(PPh3)] (4) were obtained by treatment of [AuCl(PPh3)] with the organolithium reagents LiC6F4N and LiC(6)F(4)py, respectively. However, this synthetic strategy failed for organogold compounds containing a polyphosphane ligand. Consequently, an alternative synthetic procedure, based on displacement reactions of the weakly coordinated tht ligand from [Au(C(6)F(4)py)(tht)] by the appropriate polyphosphane, was undertaken. Thus, the following complexes were isolated and characterized: [(AuC(6)F(4)py)(2)(mu(2)-diphosphane)] [diphosphane = bis(diphenylphosphanyl)methane (dppm) (9), 2,2-bis(diphenylphosphanyl)propane (dppip) (10), 1,2-bis(diphenylphosphanyl)ethane (dppe) (11), trans-1,2-bis-(diphenylphosphanyl)ethylene (dppet) (12), 1,2-bis(diphenylphosphanyl)acetylene (dppa) (13), 1,3-bis(diphenylphosphanyl)propane (dppp) (14), 1,4-bis(diphenylphosphanyl)butane (dppb) (15), 4,4'-bis(diphenylphosphanyl)-1,1'-biphenyl (dppdph) (16)1 [(AuC(6)F(4)py)(3)(mu(3)-triphosphane)] [triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane (triphos) (17), 1,3,5-tris(diphenylphosphanyl)benzene (triphosph) (18)], and [(AuC(6)F(4)py)(4)(mu(4)-tetraphosphane)] [tetraphosphane = tetra-(diphenylphosphanyl)methane (tetraphos) (19), 1,2,3,5-tetra(diphenylphosphanyl)benzene (tetraphosph) (20)]. Coordination reaction assays of compounds 1, 2, 3, and 4 with [M(diphosphane)(H2O)(2)](OTf)(2) (M = Pd, Pt) were performed in order to test their potential as building blocks in the self-assembly of discrete species. The crystal structures of compounds BrC(6)F(4)py, 1,4,17, and 19 were determined. Extensive noncovalent interations, particularly fluorine interactions such as C-F center dot center dot center dot pi(F), C-F center dot center dot center dot H, and F center dot center dot center dot F, have been found to influence the molecular packing of these species.
- 出版日期2011-6-27
