Creating Solid Solutions of Metallocenes: Migration of Nickelocene into the Ferrocene Crystal Lattice in the Absence of a Solvent
Creating Solid Solutions of Metallocenes: Migration of Nickelocene into the Ferrocene Crystal Lattice in the Absence of a Solvent
复制标题
创建茂金属固溶体：在没有溶剂的情况下茂镍迁移到二茂铁晶格中
DOI：
10.1021/acs.jpcc.2c07441
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Blümel, Janet
中科院分区：
文献类型：
--
作者：
Harmon-Welch, Gabrielle E.;Hoefler, John C.;Trujillo, Martha R.;Bhuvanesh, Nattamai;Bakhmutov, Vladimir I.;Blümel, Janet
二茂铁和茂镍在溶液中不发生反应，但顺磁成分对二茂铁~1H核磁共振信号线宽和弛豫时间的影响是定量的。二茂铁和茂镍以任何比例从溶剂中共结晶可以用两种纯物质在同一空间群P21/n中结晶来解释。作为一种新现象，当二茂铁单晶在无溶剂的情况下接触多晶茂镍时，茂镍迁移到二茂铁晶格中，形成保持宏观形状的混合晶体。这一过程已经通过切割单晶得到了直观的证明。以不同摩尔比的多晶二茂铁和多晶茂镍按不同的摩尔比与研钵混合，得到具有相应摩尔比的结晶固溶体。在没有溶剂的情况下，一种有机金属组分在常温下迁移到另一种有机金属组分的现有晶格中的过程以前没有描述过。用不同比例的二茂铁/茂镍干混合物的静态和旋转样品的顺磁1H固体核磁共振谱在分子水平上证明和定量了这两种茂金属的混合。50/50混晶的单晶X射线结构证实了核磁共振的结果，即镍茂铁和二茂铁随机分布在晶格中，空间群P21/Nis保持不变。在室温下，混合晶格中的所有二茂铁分子的~1H宽线信号和剩余魔角自旋(MAS)线都表现出展宽。二茂铁信号的展宽与镍茂铁的含量有关。通过对不同镍茂铁含量样品中二茂铁信号的弛豫时间的测量，证实了信号展宽是由于镍茂镍附近二茂铁分子的顺磁偶极-偶极驰豫所致。在一个转子中空间分离的二茂铁和镍茂金属粉末显示了单个多晶茂金属的固态核磁共振特征。所描述的在没有溶剂的情况下形成茂金属的固溶体将为获得具有期望的金属比例的均匀混合的纳米颗粒和双原子催化剂开辟新的途径。
Ferrocene and nickelocene do not react with each other in solution; however, the large impact of the paramagnetic component on the ferrocene1H NMR signal linewidth and relaxation times has been quantified. Co-crystallization of ferrocene and nickelocene at any ratio from a solvent can be explained with both pure substances crystallizing in the same space groupP21/n. As a new phenomenon, when a ferrocene single crystal is exposed to polycrystalline nickelocene in the absence of a solvent, the nickelocene migrates into the ferrocene crystal lattice and a mixed crystal is formed that retains its macroscopic shape. This process has been proven visually by cutting the single crystal. Mixing polycrystalline ferrocene with polycrystalline nickelocene at different molar ratios with a mortar and pestle leads to crystalline solid solutions with the corresponding molar ratios of both components. This migration of one organometallic component into an existing crystal lattice of another at ambient temperature in the absence of a solvent has not been described previously. Paramagnetic1H solid-state NMR spectroscopy of static and rotating samples of dry ferrocene/nickelocene mixtures at varying ratios is used to prove and quantify the mixing of both metallocenes at the molecular level. A single-crystal X-ray structure of a 50/50 mixed crystal corroborates the NMR results that nickelocene and ferrocene are randomly distributed in the lattice and that the space groupP21/nis retained. All ferrocene molecules in the mixed crystal lattice show a broadening of their1H wideline signals and residual magic-angle spinning (MAS) lines at ambient temperature. The broadening of the ferrocene signals correlates with the nickelocene content.1HT1relaxation time measurements for the signals of ferrocene in samples with different amounts of nickelocene corroborate the assumption that the signal broadening is due to paramagnetic dipole–dipole relaxation of ferrocene molecules in the vicinity of nickelocene. Spatially separated ferrocene and nickelocene powders in one rotor show the solid-state NMR characteristics of the individual polycrystalline metallocenes. The described formation of solid solutions of metallocenes in the absence of a solvent will open new pathways to homogeneously mixed nanoparticles with desired metal ratios and dual-atom catalysts.
登录
查看更多内容
两种类型的[2-(二甲氨基)乙基]环戊二烯基配体分子内路易斯碱加合物：{η5:η1-C5H4[(CH2)2NMe2]}Ni−I和{η5-μ-C5H4[的合成和晶体结构(CH2)2NMe2]}(Me3P)Ni−InI2†,‡
DOI：
--
发表时间：
1996
期刊：
影响因子：
--
作者：
R. Fischer;Sylvain Nlate;Holger Hoffmann;E. Herdtweck;J. Blümel
通讯作者：
J. Blümel
固态核磁共振波谱研究顺磁性二茂铬
DOI：
--
发表时间：
1996
期刊：
影响因子：
--
作者：
J. Blümel;M. Herker;W. Hiller;F. Köhler
通讯作者：
F. Köhler
影响因子：
4.4
作者：
Martin, Bob;Autschbach, Jochen
通讯作者：
Autschbach, Jochen
DOI：
10.1021/acs.langmuir.0c02327
发表时间：
2020
期刊：
Langmuir : the ACS journal of surfaces and colloids
影响因子：
--
作者：
I. Shenderovich
通讯作者：
I. Shenderovich
二氧化硅上膦的固定化：通过模型烷基、芳基和乙氧基鏻盐的 31P CP/MAS 研究鉴定副产物。
影响因子：
4.6
作者：
J. Sommer;Y. Yang;D. Rambow;J. Blümel
通讯作者：
J. Blümel