Department of Chemistry and Science, Materials Sciences Center, Philipps University of Marburg, 35043 Marburg, Germany.
Institute for Physical Chemistry, University of Regensburg, 93040 Regensburg, Germany.
Molecules. 2020 Sep 1;25(17):3990. doi: 10.3390/molecules25173990.
A series of dinuclear copper(I) and carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py) () and (CDP(CHPPh) () have been isolated and characterized. Detailed structural information was gained by single-crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone pairs involved in the binding of two geminal L-Cu(I) fragments at Cu-Cu distances in the range 2.55-2.67 Å. In order to enhance conformational rigidity within the characteristic Cu-C-Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py) () and its dinuclear copper complexes and , as well as two diphenylphosphinomethylene functions in ligand CDP(CHPPh) () and its di- and mononuclear complexes -. Neutral complexes were typically obtained via the reaction of with Cu(I) species CuCl, CuI, and CuSPh or via the salt elimination reaction of [(CuCl)(CDP(Py)] () with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating with two equivalents of [Cu(NCMe)]PF, followed by the addition of either two equivalents of an aryl phosphine (PPh P(CHOMe)) or one equivalent of bisphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), or 1,1'-bis(diphenyl-phosphino) ferrocene (dppf). For the first time, carbodiphosphorane CDP(CHPPh) () could be isolated upon treating its precursor [CH(dppm)]Cl () with NaNH in liquid NH. A protonated and a deprotonated derivative of ligand were prepared, and their coordination was compared to neutral CDP ligand . NMR analysis and DFT calculations reveal that the most stable tautomer of does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields () were determined to be 36% for dicationic (CuPPh)(CDP(Py)) () and 60% for neutral [(CuSPh)(CDP(CHPPh)] ().
使用多齿配体 CDP(Py)()和(CDP(CHPPh)()，已经分离并表征了一系列双核铜（I）和碳二磷（CDP）配合物。通过对九个代表性实例的单晶 XRD 分析获得了详细的结构信息。共同的结构特征是中心双亚基碳原子，其特征两个孤对电子参与在 Cu-Cu 距离为 2.55-2.67Å的两个相邻 L-Cu(I)片段的结合。为了增强特征 Cu-C-Cu 三角形内的构象刚性，两个类型的螯合侧臂对称地连接到每个磷原子上：配体 CDP(Py)()及其双核铜配合物[和]中的两个 2-吡啶基功能，以及配体 CDP(CHPPh)()及其二核和单核配合物[和]中的两个二苯膦亚甲基功能。通过与 Cu(I)物种 CuCl、CuI 和 CuSPh 反应或通过与（CuCl）（CDP(Py)与钠离子卡巴唑的盐消除反应，通常获得中性配合物。通过用二当量[Cu(NCMe)]PF处理[，然后加入二当量的芳基膦（PPhP(CHOMe)）或一当量的双膦配体双[(2-二苯基膦基)苯基]醚（DPEPhos）、4,5-双（二苯基膦基）-9,9-二甲基氧杂蒽（XantPhos）或 1,1'-双（二苯基膦基）二茂铁（dppf），制备了阳离子 Cu(I)配合物。首次通过在液氨中用 NaNH 处理其前体[CH(dppm)]Cl()，可以分离得到 carbodiphosphorane CDP(CHPPh)()。制备了配体的质子化和去质子化衍生物，并将其配位与中性 CDP 配体进行了比较。NMR 分析和 DFT 计算表明，在未配位的碱形式中，最稳定的互变异构体[不显示 CDP（或 carbone）结构。对于大多数制备的配合物，在室温下用紫外光照射时观察到光致发光。确定量子产率()为二阳离子(CuPPh)(CDP(Py))()为 36%，中性(CuSPh)(CDP(CHPPh)为 60%。
