A novel high-yield route to organic derivatives of group 2 metals; X-ray structure of [{Ba(OTf)2}4(py)14]·py (OTf = OSO2CF3) and NMR spectral characterisation of [Ba(NR2)(µ-NR2)2Na(thf)2](R = SiMe3)
摘要:
M(OTf)2[from MO + 2 HOTf; OTf = OSO2CF3 and M = Ca 1, Sr 2 or Ba 3] 与 2MOAr 或 2MNR2(M = Na 或 K,Ar = C6H2But2-2,6-Me-4;R=SiMe3)在 0 °C 的 thf 中反应,得到[Ca(OAr)2(thf)3]4、[M(OAr)2(thf)4](M=Sr 5 或 Ba 6)、[M(NR2)2(thf)2](M=Ca 7 或 Sr 8)或[Ba(NR2)(µ-NR2)2Na(thf)2]9;新化合物 1-3 在吡啶中的核磁共振光谱和 3 的吡啶加合物的 X 射线衍射表征:结晶[Ba4(η2-OTF)2(µ-OTF)2(µ3-OTF)4(py)14]-py 10 在金属三氟化物中是独一无二的,它的-OTF 配体有三种不同的成键模式。
Redox Potential and Electronic Structure Effects of Proximal Nonredox Active Cations in Cobalt Schiff Base Complexes
作者:Alexander H. Reath、Joseph W. Ziller、Charlene Tsay、Austin J. Ryan、Jenny Y. Yang
DOI:10.1021/acs.inorgchem.6b03098
日期:2017.3.20
redox potential and electronic structure of the redox active site. To explore and quantify this effect, we report the synthesis and characterization of a series of tetradentate Schiffbase ligands appended with a crown-like cavity incorporating a series of alkali and alkaline earth Lewis acidic cations (1M, where M = Na+, K+, Ca2+, Sr2+, and Ba2+) and their corresponding Co(II) complexes (2M). Cyclic voltammetry
Pyridyldiimine macrocyclic ligands: Influences of template ion, linker length and imine substitution on ligand synthesis, structure and redox properties
作者:Laura M. Thierer、Qiuran Wang、Sam H. Brooks、Peng Cui、Jia Qi、Michael R. Gau、Brian C. Manor、Patrick J. Carroll、Neil C. Tomson
DOI:10.1016/j.poly.2021.115044
日期:2021.4
derived from the Npyr-M-Npyr bond angle and the relative orientation of the pyridinediimine (PDI) and pyridinedialdimine (PDAI) fragments to each other within the solid state structures. Cyclic voltammetry and UV-Vis spectroscopy were used to compare the relative energies of the imine π* orbital of the redoxactive PDI and PDAI components in the macrocycle when coordinated to redox inactive metals. Both
Two-step modulation of ion recognition using a bis(saloph)-macrocyclic host having a 24-crown-8-like cavity
作者:Yoko Sakata、Seiya Kobayashi、Shigehisa Akine
DOI:10.1039/c7cc02641b
日期:——
Precise modulation of cation binding affinity was accomplished by the efficient two-step conversion of a newly synthesized macrocyclic ligand H4L2 having a 24-crown-8-like cavity and two saloph moieties. The conversion of H4L2 into L2Ni2 resulted in a 120-fold enhancement in the binding affinity towards Cs+. The electrochemical reduction of L2Ni2 further enhanced the recognition ability by 3 orders
阳离子结合亲和力的精确调节是通过新合成的具有24冠8样腔和两个saloph部分的大环配体H 4 L 2的有效两步转化来实现的。H 4 L 2转化为L 2 Ni 2导致对Cs +的结合亲和力提高了120倍。L 2 Ni 2的电化学还原进一步将识别能力提高了3个数量级。
On the Use of Aqueous Metal-Aqua p<i>K</i><sub>a</sub> Values as a Descriptor of Lewis Acidity
作者:Amit Kumar、James D. Blakemore
DOI:10.1021/acs.inorgchem.0c03239
日期:2021.1.18
The behavior of Lewis acidic metal ions in multimetallic systems has become a subject of intense interest in recent years. Parametrizing the behavior of these ions in nonaqueous conditions, commonly used in the field, is challenging due to the lack of direct measures of the Lewisacidity of metal ions in polar organic solvents. Here, we report the use of triphenylphosphine oxide (TPPO) as a 31P nuclear
近年来,路易斯酸性金属离子在多金属体系中的行为已成为人们关注的焦点。由于缺乏直接测量极性有机溶剂中金属离子的路易斯酸度的方法,因此在本领域中常用的在非水条件下对这些离子的行为进行参数化具有挑战性。在这里,我们报告使用三苯膦氧化物(TPPO)作为31 P核磁共振(NMR)探针,使用Gutmann-Beckett方法定量金属三氟甲磺酸盐库的Lewis酸度。相应的金属水族物种[ M(H 2 O)m ] n +的p K a值的图,以H 2 O对这些金属在氘代乙腈(d 3 -MeCN)和氘代二氯甲烷(CD 2 Cl 2)中的存在下,TPPO的31 P NMR位移显示出紧密的共线性关系,表明这些离子在水中的相似行为d 3 -MeCN,和CD 2 Cl 2。这种共线性增强了使用水性p K a值作为路易斯酸度描述子的通用方法的实用性,而与在立即实验中使用的溶剂无关,并提供了对该描述子在广泛应用中的有用性的认识。d
Ring-Size-Modulated Reactivity of Putative Dicobalt-Bridging Nitrides: C−H Activation versus Phosphinimide Formation
作者:Peng Cui、Qiuran Wang、Samuel P. McCollom、Brian C. Manor、Patrick J. Carroll、Neil C. Tomson
DOI:10.1002/anie.201708966
日期:2017.12.11
Dicobalt complexes supported by flexible macrocyclic ligands were used to target the generation of the bridging nitrido species [(nPDI2)Co2(μ‐N)(PMe3)2]3+ (PDI=2,6‐pyridyldiimine; n=2, 3, corresponding to the number of catenated methylene units between imino nitrogen atoms). Depending on the size of the macrocycle and the reaction conditions (solution versus solid‐state), the thermolysis of azide precursors