Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2
Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2
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由四膦三桥联的双核铜配合物，rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2
DOI：
10.1002/ejic.201900785
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发表时间：
2019
影响因子：
2.3
通讯作者：
Nakajima Takayuki
中科院分区：
文献类型：
--
作者：
Tanase Tomoaki;Otaki Risa;Okue Ayumi;Nakamae Kanako;Nakajima Takayuki
[Cu（MeCN）4] BF 4与rac-Ph 2 PCH 2 P（Ph）CH 2 P（Ph）CH 2 PPh 2（rac-dpmppm）反应生成[Cu 2（μ-rac-dpmppm）（MeCN）4]（BF 4）2（1），CuCl与rac-dpmppm在2，6-二甲苯基异腈（XylNC）和NH 4PF 6存在下反应生成[Cu 2（μ-rac-dpmppm）（XylNC）4]（PF 6）2（2）。配合物1用二亚氨基配体（N^N）处理，得到一系列CuI 2配合物[Cu 2（μ-rac-dpmppm）（N^N）2]2+（N^N = phen（3），4-Mephen（4），4，7-Me2phen（5），5，6-Me2phen（6），2，9-Me2phen（7），3，4，7，8-Me4phen（8），4，7-Ph2phen（9），bpy（10），4，4 ′-Me2bpy（11），和1，8-萘啶（nap）（12）），其中phen = 1，10-菲咯啉，bpy = 2，2 ′-联吡啶。通过光谱和X射线晶体学分析对分离的配合物进行了表征，结果表明两个Cu离子通过arac-dpmpm配体以κ2，κ 2方式三重桥接，形成了坚固的Z-型双铜结构，其中Cu···Cu距离在4.2到5.6 nm之间变化，这取决于辅助配体通过改变稠合六元螯合环的构象。XylNC和2，9-Me 2 phen的大体积配体使构象变形为船（2）和扭曲船（7）形式，导致Cu···Cu分离延长（Cu···Cu = 5.3488（5）Å（2），5.5681（6）Å（7）），和其他非大体积配体使它们成为变形的椅子形式，Cu···Cu = 4.2051（5）<$（8）至4.7341（5）<$（10）。通过变温1H NMR研究了化合物5和11的溶液行为，发现室温下四面体Cu中心上的两个氮原子发生了流动交换，ΔG ε为14 kcal/mol. 3 - 12的光物理性质也进行了研究，显示快速荧光在394-467 nm的二氯甲烷溶液和磷光在582-608 nm的固态。[Cu（MeCN）4] BF 4与rac-dpmppm和NaBH 4在MeOH/CHCl 3中反应得到[Cu 4（µ4-H）（µ-Cl）2（µ-rac-dpmppm）2] BF 4（13），其中tworac-dpmppm配体表现出κ2，κ1，κ 1 M3-桥的新配位模式，两个{Cu 2（µ-Cl）（µ-rac-dpmppm）}+单元通过中心的µ4-氢化物连接。
Reaction of [Cu(MeCN)4]BF4withrac‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2(rac‐dpmppm) gave [Cu2(µ‐rac‐dpmppm)(MeCN)4](BF4)2(1), and that of CuCl withrac‐dpmppm in the presence of 2,6‐xylyl isocyanide (XylNC) and NH4PF6afforded [Cu2(µ‐rac‐dpmppm)(XylNC)4](PF6)2(2). Complex1was converted by treatment with diimino ligands (N^N) to a series of CuI2complexes, [Cu2(µ‐rac‐dpmppm)(N^N)2]2+(N^N = phen (3), 4‐Mephen (4), 4,7‐Me2phen (5), 5,6‐Me2phen (6), 2,9‐Me2phen (7), 3,4,7,8‐Me4phen (8), 4,7‐Ph2phen (9), bpy (10), 4,4′‐Me2bpy (11), and 1,8‐naphtyridine (nap) (12)), where phen = 1,10‐phenanthroline and bpy = 2,2′‐bipyridyl. The isolated complexes were characterized by spectroscopic and X‐ray crystallographic analyses to reveal that two CuIions are triply bridged by arac‐dpmppm ligand in κ2,κ2fashion resulting in robustZ‐form dicopper structures, where the Cu···Cu distances vary from 4.2 to 5.6 Å depending on the ancillary ligands through altering conformation of the fused six‐membered chelate rings. The bulky ligands of XylNC and 2,9‐Me2phen deform the conformation to boat (2) and twist boat (7) forms, leading to elongation of Cu···Cu separation (Cu···Cu = 5.3488(5) Å (2), 5.5681(6) Å (7)), and other non‐bulky ligands render them deformed chair forms with Cu···Cu = 4.2051(5) Å (8) to 4.7341(5) Å (10). The solution behaviors of5and11were examined by variable temperature1H NMR measurements to show fluxional exchange of the two nitrogen atoms attaching to the tetrahedral Cu centers with ΔG‡of 14 kcal/mol at room temperature. Photophysical properties of3–12were also investigated to show rapid fluorescence at 394–467 nm in CH2Cl2solutions and phosphorescence at 582–608 nm in the solid states. Reaction of [Cu(MeCN)4]BF4withrac‐dpmppm and NaBH4in MeOH/CHCl3afforded [Cu4(µ4‐H)(µ‐Cl)2(µ‐rac‐dpmppm)2]BF4(13), in which tworac‐dpmppm ligands exhibited a new coordination mode of κ2,κ1,κ1M3‐bridge to hold two {Cu2(µ‐Cl)(µ‐rac‐dpmppm)}+units connected by a central µ4‐hydride.