Cationic dinuclear Pd-allyl-halide complexes with N-heterocyclic carbenes
Cationic dinuclear Pd-allyl-halide complexes with N-heterocyclic carbenes
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DOI：
10.1021/om049317o
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发表时间：
2005-01-31
期刊：
影响因子：
2.8
通讯作者：
Pörschke, KR
中科院分区：
文献类型：
--
作者：
Ding, YQ;Goddard, R;Pörschke, KR
单核N-杂环卡宾配合物（eta（3）-C3 H5）Pd{C（N（R）CH）（2）}X（R = Bu-t，X = Cl，I（1ab）; R = C6H3- 2，6-Pr-1（2），X = Cl，I（2ab））与TIPF 6和TlOTf在CH 2Cl 2或THF中的反应导致部分卤化物取代，得到离子双核配合物[{（eta（3）-C3 H5）Pd（C（N（R）CH）（2））}（2）（mu-X）]Y（R = Bu-t，X = Cl，Y = PF6（3a），OTf（3b）和X = I，Y = OTf（3c）; R = C6H3- 2，6-Pr-i（2），X = Cl，Y = PF6（4a），OTf（4b）和X = I，Y = OTf（4c））。根据溶液NMR，双核配合物作为非对映异构体的混合物存在。用X射线晶体学方法测定了3a-0.5（C_4H_（10）O）·0.5（CH_2Cl_2）的晶体结构。由2a与LiMe反应得到PdMe衍生物（eta（3）-C_3H_5）Pd{C（N（C_6H_3 - 2，6-Pr ~（1（2））CH）（2）}Me（6）。当Ia与B（C6 F5）（3）反应时，NHC配体被转移以得到（C6 F5）（3）B-C（N（Bu-t）CH）（2）和起始物{（eta（3）-C3 H5）Pd（μ-Cl）}（2）。
Reaction of the mononuclear N-heterocyclic carbene complexes (eta(3) -C3H5)Pd{C(N(R)CH)(2)}X (R = Bu-t, X = Cl, I (1ab); R = C6H3-2,6-Pr-i(2), X = Cl, I (2ab)) with TIPF6 and TlOTf in CH2Cl2 or THF results in partial halide substitution to afford the ionic dinuclear complexes [{(eta(3) -C3H5)Pd(C(N(R)CH)(2))}(2)(mu-X)]Y (R = Bu-t, X = Cl, Y = PF6 (3a), OTf (3b) and X = I, Y = OTf (3c); R = C6H3-2,6-Pr-i(2), X = Cl, Y = PF6 (4a), OTf (4b) and X = I, Y = OTf (4c)). According to solution NMR the dinuclear complexes are present as mixtures of diastereorners. The crystal structure of 3a-0.5(C4H10O).0.5(CH2Cl2) has been determined by X-ray crystallography. From the reaction of 2a with LiMe the PdMe derivative (eta(3)-C3H5)Pd{C(N(C6H3-2,6-Pr-i(2))CH)(2)}Me (6) has been obtained. When la was reacted with B(C6F5)(3), the NHC ligand was transferred to give (C6F5)(3)B-C(N(Bu-t)CH)(2) and the starting {(eta(3) -C3H5)Pd(mu-Cl)}(2).