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Synthesis, structures and reactions of new cyclometallated dinuclear gold complexes containing the fluorine-substituted ligands

机译:含有氟取代配体的新型环金属化双核金配合物的合成,结构和反应

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摘要

The dinuclear cyclometallated gold(I) complex [Au2(μ-2-C6F4PPh2)2] was prepared in high yield from the reaction of 2-LiC6F4PPh2 with either [AuBr(AsPh3)] or [AuCl(tht)], and from the reaction of 2-Me3SnC6F4PPh2 with [AuCl(tht)]. The digold(I) complex undergoes oxidative addition reactions with halogens to give the metal-metal bonded dihalodigold(II) complexes [Au2IIX2(μ-2-C6F4PPh2)2] (X = Cl, Br, I), which on warming or exposure to light, isomerise to give the heterovalent gold(I)-gold(III) species [XAu(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuX] containing a four-membered cyclometallated ring on a gold(III) centre. Unlike its protio analogue, [Au2(μ-2-C6F4PPh2)2] did not undergo oxidative addition of methyl iodide or dibenzoyl peroxide. The dihalodigold(II) [Au2IIX2(μ-2-C6F4PPh2)2] and gold(I)-gold(III) compounds [XAu(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuX] (X = Cl, Br) are further oxidised by halogens to give the digold(III) species [Au2X4(μ-2-C6F4PPh2)2] and [X3Au(μ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuX], respectively. The complexes [Au2X4(μ-2-C6F4PPh2)2] are reduced to the dihalodigold(II) complexes in the presence of one equivalent of zinc powder; further addition of zinc gave the parent digold(I) dimer. Treatment of [Au2IICl2(μ-2-C6F4PPh2)2] and [ClAu(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuCl] with an excess of silver nitrate, benzoate, acetate, trifluoroacetate or triflate gave the corresponding oxyanion complexes. Slow crystallisation of the di(benzoato)digold(II) complex from dichloromethane and methanol gave the parent digold(I) complex derived by reductive elimination. The di(triflato)digold(II) complex behaved similarly, although in this case the novel gold(I) tetramer [Au4(μ-2-C6F4PPh2)4] was formed together with the dimer. Two closely related gold complexes containing the chelating κ2(C,O) phosphine oxide ligand, 2-C6F4P(O)PPh2, were isolated from the reaction of [ClAu(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuCl] with an excess of silver nitrate. The reaction of [Au2IICl2(μ-2-C6F4PPh2)2] with two equivalents of potassium trifluoroethoxide failed to give the corresponding digold(II) bis(alkoxo) complex; instead, reduction took place to form the digold(I) dimer [Au2(μ-2-C6F4PPh2)2]. Treatment of a solution of the di(benzoato)digold(II) complex with C6F5Li gave the pentafluorophenyl complex [Au2(C6F5)2(μ-2-C6F4PPh2)2] which, when heated in toluene, rearranged to the gold(I)-gold(III) complex [(C6F5)Au(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)Au(C6F5)], analogous to the behaviour of the dihalodigold(II) complexes. The heterovalent, gold(I)-gold(III) dimethyl compound [Au2I,III(CH3)2(μ-2-C6F4PPh2)2] was obtained from the reaction of the di(benzoato)digold(II) complex with dimethylzinc. This compound is structurally similar to its tetraprotio analogue. The cycloaurated dinuclear gold complexes [Au2(μ-C6H3-n-F-2-PPh2)2] (n = 5, 6) were made similarly to the 2-C6F4PPh2 analogue from the appropriate lithium or tin reagents, though in some cases the dimers were formed in admixture with the corresponding gold(I) tetramers. Like their tetrafluoro analogues, the 6-fluoro complexes [Au2X2(μ-C6H3-6-F-2-PPh2)2] (X = Cl, Br, I) rearrange on heating to give the heterovalent gold(I)-gold(III) species [XAu(µ-C6H3-6-F-2-PPh2)(κ2-C6H3-6-F-2-PPh2)AuX]. Thus, the presence of a fluorine atom in place of hydrogen in the 6-position of the bridging aryl group is sufficient to stop the isomerisation of the digold(II) complexes [Au2X2(μ-2-C6H4PPh2)2] at the gold(I)-gold(III) stage and to prevent subsequent C-C coupling of the aryl groups at the gold(III) centre. In contrast, the dihalodigold(II) complexes containing the 5-fluoro substituted ligand undergo reductive elimination and coupling of the metallated aryl groups to give the digold(I) biphenyldiyl complexes [Au2X2(2,2'-Ph2P-5-FC6H3C6H3-5-F-PPh2)] (X = Cl, Br, I). The described complexes were characterised using 1H NMR, 31P NMR, 19F NMR spectroscopy, elemental analysis, mass spectroscopy, IR spectroscopy, X-ray diffraction and 197Au Mössbauer spectroscopy.
机译:通过2-LiC6F4PPh2与[AuBr(AsPh3)]或[AuCl(tht)]的反应,并由高能制备双核环金属化金(I)络合物[Au2(μ-2-C6F4PPh2)2]。 2-Me3SnC6F4PPh2与[AuCl(tht)]的反应。 digold(I)配合物与卤素发生氧化加成反应,得到金属-金属键合的二卤代二金(II)配合物[Au2IIX2(μ-2-C6F4PPh2)2](X = Cl,Br,I),在加热或暴露后会发生这种反应光照后,异构化,得到在金(III)中心包含四元环金属化环的杂价金(I)-金(III)种类[XAu(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuX] 。与它的蛋白质类似物不同,[Au2(μ-2-C6F4PPh2)2]没有进行甲基碘或过氧化二苯甲酰的氧化加成。二卤代金(II)[Au2IIX2(μ-2-C6F4PPh2)2]和金(I)-金(III)化合物[XAu(μ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuX](X = Cl, Br)进一步被卤素氧化,分别得到dig(III)种类[Au2X4(μ-2-C6F4PPh2)2和[X3Au(μ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuX]。在一当量的锌粉存在下,将配合物[Au2X4(μ-2-C6F4PPh2)2]还原为二卤代金(II)配合物;进一步添加锌得到母体digold(I)二聚体。用过量的硝酸银,苯甲酸盐,乙酸盐,三氟乙酸盐或三氟甲磺酸盐处理[Au2IICl2(μ-2-C6F4PPh2)2]和[ClAu(μ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuCl],得到相应的氧阴离子复合体。从二氯甲烷和甲醇中缓慢结晶出二(苯并氨基)digold(II)配合物,通过还原消除得到母体digold(I)配合物。尽管在这种情况下,新型金(I)四聚体[Au4(μ-2-C6F4PPh2)4]与二聚体一起形成,但二(三氟代)二甲双胍(II)的行为相似。从[ClAu(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuCl]的反应中分离出两个密切相关的含螯合κ2(C,O)氧化膦配体的金络合物2-C6F4P(O)PPh2。与过量的硝酸银。 [Au2IICl2(μ-2-C6F4PPh2)2]与两当量的三氟乙氧基钾反应未能得到相应的二甲双(烷氧基)络合物。取而代之的是还原反应生成二聚体(I)二聚体[Au2(μ-2-C6F4PPh2)2]。用C6F5Li处理二苯并二甲双胍(II)配合物的溶液得到五氟苯基配合物[Au2(C6F5)2(μ-2-C6F4PPh2)2],当在甲苯中加热时,重排成金(I) -金(III)络合物[(C6F5)Au(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)Au(C6F5)],类似于二卤二金(II)络合物的行为。异价的金(I)-金(III)二甲基化合物[Au2I,III(CH3)2(μ-2-C6F4PPh2)2]是由二(苯并基)二甲双胍(II)配合物与二甲基锌反应制得的。该化合物在结构上类似于其四氢类似物。用合适的锂或锡试剂类似于2-C6F4PPh2类似物制备了环化双核金络合物[Au2(μ-C6H3-nF-2-PPh2)2](n = 5、6),尽管在某些情况下为二聚体它们与相应的金(I)四聚体混合形成。像它们的四氟类似物一样,6-氟配合物[Au2X2(μ-C6H3-6-F-2-PPh2)2](X = Cl,Br,I)在加热时会重排,得到杂价金(I)-金( III)种[XAu(μ-C6H3-6-F-2-PPh2)(κ2-C6H3-6-F-2-PPh2)AuX]。因此,在桥连的芳基的6位上存在一个氟原子代替氢,足以阻止金([au2X2(μ-2-C6H4PPh2)2] I)-金(III)阶段,并防止随后在金(III)中心的芳基进行CC偶联。相反,含有5-氟取代的配体的二卤二金(II)配合物经过还原消除并偶合了金属化的芳基,从而得到二甲双(I)联苯二基配合物[Au2X2(2,2'-Ph2P-5-FC6H3C6H3-5 -F-PPh2)](X = Cl,Br,I)。使用1H NMR,31P NMR,19F NMR光谱,元素分析,质谱,IR光谱,X射线衍射和197Au Mssbauer光谱对所描述的络合物进行表征。

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    Mirzadeh N;

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