Ai Pengfei, Gourlaouen Christophe, Danopoulos Andreas A, Braunstein Pierre
Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg , 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France.
Laboratoire de Chimie Quantique, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg , 1 rue Blaise Pascal, 67008 Strasbourg, France.
Inorg Chem. 2016 Feb 1;55(3):1219-29. doi: 10.1021/acs.inorgchem.5b02382. Epub 2016 Jan 20.
The reaction of the trinuclear complex Ag3(μ3-PC(NHC)P,κP,κC(NHC),κP)23 (Ag3; PC(NHC)P = N,N'-bis(di-tert-butylphosphanyl)imidazol-2-ylidene) with [Pd(dba)2] afforded the trinuclear palladium complex Pd3(μ3-PC(NHC)P,κP,κC(NHC),κP)22 (Pd3) and the dinuclear palladium(I) complex Pd2(μ2-PC(NHC)P,κP,κC(NHC),κP)22 (Pd2). The assignment of the oxidation state of the metals in the mixed-valence Pd3 chain as Pd(0)-Pd(II)-Pd(0) was based on the reactivity of the complex with 2,6-dimethylphenyl isocyanide and density functional theory calculations. Reaction of PCNHCP with [PdMe2(tmeda)] afforded the palladium(II) complex [PdMe2(PC(NHC)P,κP,κC(NHC))] (Pd-Me2), with PC(NHC)P acting as a bidentate ligand. The reaction of PC(NHC)P with [Pd(dba)2] led to a dinuclear palladium(0) complex Pd2(μ2-PC(NHC)P,κP,κC(NHC),κP) (Pd2-dba); attempted replacement of the remaining dba by PC(NHC)P failed. The imidazolium triflate PCHP, precursor to PC(NHC)P, was reacted with [Pd2(dba)3]·CHCl3 to give the (2 + 2) metalla-mesocyclic cationic palladium(0) complex [Pd2(μ2-PCHP,κP,κP)2] (PCHP-Pd2), which resisted further deprotonation of the imidazolium cation. In contrast, PCHP reacted with [AuCl(tht)] to give [Au2Cl2(μ2-PCHP,κP,κP)] (PCHP-Au2), in which one Au-Cl moiety is bound to each P donor. Further reaction of PCHP-Au2 with [Au{N(SiMe3)2}(PPh3)] afforded a mixture of the trinuclear Au3(μ3-PC(NHC)P,κP,κC(NHC),κP)23 (Au3) and [AuCl(PPh3)], while reaction with [CuMes]5, where Mes = 2,4,6-trimethylphenyl, resulted in a novel, centrosymmetric, heterometallic complex [Au2Mes2(Cu4Cl4)(PCHP,κP,κP)2] (PCHP-AuCu) featuring a new PCHP-AuMes metalloligand bridging a Cu···Cu diagonal of a Cu4Cl4 cubane via the P and AuMes functionalities.
三核配合物Ag3(μ3-PC(NHC)P,κP,κC(NHC),κP)23（Ag3；PC(NHC)P = N,N'-双（二叔丁基膦基）咪唑-2-亚基）与[Pd(dba)2]反应，得到三核钯配合物Pd3(μ3-PC(NHC)P,κP,κC(NHC),κP)22（Pd3）和双核钯（I）配合物Pd2(μ2-PC(NHC)P,κP,κC(NHC),κP)22（Pd2）。混合价态Pd3链中金属的氧化态指定为Pd(0)-Pd(II)-Pd(0)，这是基于该配合物与2,6-二甲基苯基异氰化物的反应性以及密度泛函理论计算。PCNHCP与[PdMe2(tmeda)]反应得到钯（II）配合物[PdMe2(PC(NHC)P,κP,κC(NHC))]（Pd-Me2），其中PC(NHC)P作为双齿配体。PC(NHC)P与[Pd(dba)2]反应生成双核钯（0）配合物Pd2(μ2-PC(NHC)P,κP,κC(NHC),κP)（Pd2-dba）；尝试用PC(NHC)P取代剩余的dba失败。PC(NHC)P的前体咪唑鎓三氟甲磺酸盐PCHP与[Pd2(dba)3]·CHCl3反应，得到（2 + 2）金属-中环阳离子钯（0）配合物[Pd2(μ2-PCHP,κP,κP)2]（PCHP-Pd2），该配合物能抵抗咪唑鎓阳离子的进一步去质子化。相比之下，PCHP与[AuCl(tht)]反应得到[Au2Cl2(μ2-PCHP,κP,κP)]（PCHP-Au2），其中一个Au-Cl部分与每个P供体相连。PCHP-Au2与[Au{N(SiMe3)2}(PPh3)]进一步反应，得到三核Au3(μ3-PC(NHC)P,κP,κC(NHC),κP)23（Au3）和[AuCl(PPh3)]的混合物，而与[CuMes]5（其中Mes = 2,4,6-三甲基苯基）反应，得到一种新型的、中心对称的异金属配合物[Au2Mes2(Cu4Cl4)(PCHP,κP,κP)2]（PCHP-AuCu），其特征是一种新的PCHP-AuMes金属配体通过P和AuMes官能团桥接Cu4Cl4立方烷的Cu···Cu对角线。
