Oxidative addition of small molecules to a dinuclear Au(I) amidinate complex, AU2[(2,6-Me2Ph)2N2CH]2. Syntheses and characterization of Au(II) amidinate complexes including one which possesses Au(II)-Oxygen bonds
Oxidative addition of small molecules to a dinuclear Au(I) amidinate complex, AU2[(2,6-Me2Ph)2N2CH]2. Syntheses and characterization of Au(II) amidinate complexes including one which possesses Au(II)-Oxygen bonds
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DOI：
10.1021/ic700929e
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发表时间：
2007-11-12
影响因子：
4.6
通讯作者：
Fackler, John P., Jr.
中科院分区：
文献类型：
--
作者：
Abdou, Hanan E.;Mohamed, Ahmed A.;Fackler, John P., Jr.
双核Au（I）脒基配合物Au（2）（2，6-Me 2 Ph-形式）（2）（1）通过（THT）AuCl和2，6-Me 2 Ph-形式的钾盐以1：1的化学计量比反应以定量产率分离。各种试剂如Cl-2、Br-2、I-2、CH（3）l和过氧化苯甲酰与双核Au（I）脒基络合物Au（2）（2，6-Me 2 Ph-形式）（2）加成，形成氧化加成Au（II）金属-金属键合络合物2、3、4、5和6。Au（II）脒基配合物在室温下作为固体是稳定的。报道了双核Au-2（2，6-Me_2Ph-型）（2）和Au（Ⅱ）氧化加成产物Au-2（2，6-Me_2Ph-型）（2）X-2的结构，X = Cl，Br，I.在同一晶胞中具有等量氧化和未氧化络合物的结晶产物[Au-2（2，6-Me 2 Ph-form）（2）X-2][Au-2（2，6-Me 2 Ph-form）（2）]，X = Cl，2 m，或Br，3 m，被分离并给出了它们的结构。[Au-2（2，6-Me 2 Ph-形式）（2）X-2][Au-2（2，6-Me 2 Ph-形式）（2）]（X = Cl）的结构具有比在完全氧化产物Au-2（2，6-Me-2-形式）（2）Cl-2中观察到的稍长的Au（II）-Au（II）距离，0.05 A。双核配合物中的金-金距离在与卤素的氧化加成后从2.7 A减小到2.5 A，类似于用Au（I）二硫代硫酸盐和叶立德所做的观察。过氧化苯甲酰的氧化加成导致分离出第一个具有Au-O键的稳定双核Au（II）氮配合物，即Au-2（2，6-Me 2 Ph-形式）（2）（PhCOO）（2），6，具有已知Au（II）脒配合物的最短Au-Au距离，2.48 A。该结构由通过氧连接到Au（II）中心的单齿苯甲酸酯单元组成。3中的溴化物被氯化物取代，6中的苯甲酸酯基团被氯化物或溴化物取代也很容易发生。对于1，晶胞尺寸为A = 7.354（6）a，B = 9.661（7）A，c 11.421（10）A，β = 81.74（5）度，β = 71.23（5）度，α = 86.07（9）度（棒上空间群P（1），Z = 1），对于2个中心点1.5C（6）H（12），α = 11.012（2）A，α = 18.464（4）A，c = 19.467（4）A，α = 90度，β = 94.86（3）度，gamma = 90度（空间群P2（1）/c，Z = 4），对于2 m中心点ClCH 2CH 2Cl，a = 16.597（3）A，B = 10.606（2）A，c = 19.809（3）A，α = 90度，β = 94.155（6）度，和γ = 90度（空间群P2（1）/n，Z = 2），对于3 m，a 16.967（3）A，B = 10.783（2）A，c = 20.060（4）A，α = 90度，β = 93.77（3）度，和γ = 90度（空间群P2（1）/n，Z = 2），对于4个中心点THF，a = 8.0611（12）A，B = 10.956（16）A，c = 11.352（17）A，α = 84.815（2）度，β = 78.352（2）度，伽马= 88.577（2）度（空间群P（1）在棒上，Z = 1），对于5，a = 16.688 A，B = 10.672（4）A，c = 19.953（7）A，α = 90.00（6）度，β = 94.565（7）度，伽马= 90.00度（空间群P2（1）/n，Z = 4），对于6个中心点0.5C（7）H（8），a = 11.160（3），A，B 12.112（3）A，c = 12.364（3）A，α = 115.168（4）度，β = 161.112（4）度和γ = 106.253（5）度（棒上空间群P（1），Z =1）。
The dinuclear Au(I) amidinate complex AU(2)(2,6-Me2Ph-form)(2) (1) is isolated in quantitative yield by the reaction of (THT)AuCl and the potassium salt of 2,6-Me2Ph-form in a 1:1 stoichiometric ratio. Various reagents such as Cl-2, Br-2, I-2, CH(3)l, and benzoyl peroxide add to the dinuclear Au(I)amidinate complex AU(2)(2,6-Me2Ph-form)(2) to form oxidative-addition Au(II) metal-metal-bonded complexes 2, 3, 4, 5, and 6. The Au(II) amidinate complexes are stable as solids at room temperature. The structures of the dinuclear Au-2(2,6-Me2Ph-form)(2) and the Au(II) oxidative-addition products Au-2(2,6-Me2Ph-form)(2)X-2, X = Cl, Br, I, are reported. Crystalline products with an equal amount of oxidized and unoxidized complexes in the same unit cell, [Au-2(2,6-Me2Ph-form)(2)X-2][Au-2(2,6-Me2Ph-form)(2)], X = Cl, 2m, or Br, 3m, are isolated and their structures are presented. The structure of [Au-2(2,6-Me2Ph-form)(2)X-2][Au-2(2,6-Me2Ph-form)(2)], X = Cl has a Au(II)-Au(II) distance slightly longer, 0.05A, than that observed in the fully oxidized product Au-2(2,6-Me-2-form)(2)Cl-2, 2. The gold gold distance in the dinuclear complex decreases upon oxidative addition with halogens from 2.7 to 2.5 A, similar to observations made with the Au(I) dithiolates and ylides. The oxidative addition of benzoyl peroxide leads to the isolation of the first stable dinuclear Au(II) nitrogen complex possessing Au-O bonds, Au-2(2,6-Me2Ph-form)(2)(PhCOO)(2), 6, with the shortest Au-Au distance known for Au(II) amidinate complexes, 2.48 A. The structure consists of unidentate benzoate units linked through oxygen to the Au(II) centers. The replacement of the bromide in 3 by chloride, and the benzoate groups in 6 by chloride or bromide also occurs readily. The unit cell dimensions are, for 1, A = 7.354(6) a, b = 9.661(7) A, c 11.421(10) A, = 81.74(5)degrees, beta = 71.23(5)degrees, and alpha = 86.07(9)degrees (space group P (1) over bar, Z = 1), for 2 center dot 1.5C(6)H(12), a = 11.012(2) A, alpha = 18.464(4) A, c = 19.467(4) A, alpha = 90 degrees, beta = 94.86(3)degrees, and gamma = 90 degrees (space group P2(1)/c, Z = 4), for 2m center dot ClCH2CH2Cl, a = 16.597(3) A, b = 10.606(2) A, c = 19.809(3) A, alpha = 90 degrees, beta = 94.155(6)degrees, and gamma = 90 degrees (space group P2(1)/n, Z = 2), for 3m, a 16.967(3) A, b = 10.783(2) A, c = 20.060(4) A, alpha = 90 degrees, beta = 93.77(3)degrees, and gamma = 90 degrees (space group P2(1)/n, Z = 2), for 4 center dot THF, a = 8.0611(12) A, b = 10.956(16) A, c = 11.352(17) A, alpha = 84.815(2)degrees, beta= 78.352(2)degrees, and gamma= 88.577(2)degrees (space group P (1) over bar, Z = 1), for 5, a = 16.688 A, b = 10.672(4) A, c = 19.953(7) A, alpha = 90.00 (6)degrees, beta = 94.565(7)degrees, and gamma = 90.00 degrees (space group P2(1)/n, Z = 4), for 6 center dot 0.5C(7)H(8), a = 11.160(3), A, b 12.112(3) A, c = 12.364(3) A, alpha = 115.168(4)degrees, beta = 161.112(4)degrees, and gamma = 106.253(5)degrees (space group P (1) over bar, Z =1).