Design and Synthesis of Polytopic Metalloligands Based on Fluoroaryl Gold(I) Organometallic Compounds

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.