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

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• 作者：Montserrat Ferrer ; Albert Gutie虂rrez ; Mounia Mounir ; Laura Rodri虂guez ; Oriol Rossell ; Merce虁 Font-Bardia ; Pilar Go虂mez-Sal ; Avelino Marti虂n ; Xavier Solans
• 刊名：Organometallics
• 出版年：2011
• 出版时间：June 27, 2011
• 年：2011
• 卷：30
• 期：12
• 页码：3419-3429
• 全文大小：1123K
• 年卷期：v.30,no.12(June 27, 2011)
• ISSN：1520-6041

文摘

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 NBu₄[Au(C₆F₄py)₂] (2) were obtained by reacting [AuCl(tht)] (tht = tetrahydrothiophene) with the organolithium derivatives of BrC₅F₄N and BrC₆F₄py, respectively. This route required the previous synthesis of the new fluorinated compound BrC₆F₄py, which was produced by a Stille cross-coupling between (4-pyridyl)trimethylstannane and 1,4-dibromotetrafluorobenzene. The neutral phosphane compounds [Au(C₆F₄N)(PPh₃)] (3) and [Au(C₆F₄py)(PPh₃)] (4) were obtained by treatment of [AuCl(PPh₃)] with the organolithium reagents LiC₆F₄N and LiC₆F₄py, 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(C₆F₄py)(tht)] by the appropriate polyphosphane, was undertaken. Thus, the following complexes were isolated and characterized: [(AuC₆F₄py)₂(渭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鈥?bis(diphenylphosphanyl)-1,1鈥?biphenyl (dppdph) (16)], [(AuC₆F₄py)₃(渭₃-triphosphane)] [triphosphane = 1,1,1-tris(diphenylphosphanylmethyl)ethane (triphos) (17), 1,3,5-tris(diphenylphosphanyl)benzene (triphosph) (18)], and [(AuC₆F₄py)₄(渭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 BrC₆F₄py, 1, 4, 17, and 19 were determined. Extensive noncovalent interations, particularly fluorine interactions such as C鈥揊路路路蟺_F, C鈥揊路路路H, and F路路路F, have been found to influence the molecular packing of these species.