{"title":"磷基三(2-吡啶氨基)硫膦配体的六配位 Cu (II) 复合物及其酸催化水解的合成、表征、晶体结构测定和 DFT 研究","authors":"Aswini Kalita , Lakhminandan Goswami , Pankaj Gogoi , Subrata Paul","doi":"10.1016/j.ica.2024.122408","DOIUrl":null,"url":null,"abstract":"<div><div>One mono nuclear copper(II) complex (Cu-TPPS-OOCCH<sub>3</sub> with structural formula C<sub>17</sub>H<sub>19</sub>CuN<sub>6</sub>O<sub>3</sub>PS) is synthesized using a novel tripodal tetradentate ligand, tris-(2-pyridinylamino)phosphene sulphide (TPPS), which has three pyridinylamino groups attached to a phosphorus atom connected to a sulphur atom (P<img>S). The equatorial positions of the complex are occupied by three amino <em>N</em>-atoms of three aminopyridyl groups and one O-atom of the acetate group. The apical position is occupied by other O-atom of acetate group and one secondary <em>N</em>-atom of the tripodal ligand. The complex has been synthesized and purified as green solid and characterized by various spectroscopic techniques and the structure has been determined by X-ray single crystal diffraction study. The geometry optimizations and calculations of energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the compounds are performed by using the hybrid B3LYP density functional theory (DFT) along with the def2TZVP basis set.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122408"},"PeriodicalIF":2.7000,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis, Characterization, Crystal structure determination and DFT study of a six coordinated Cu (II) complex of a phosphorous based tris-(2-pyridinylamino) phosphene sulphide ligand and its acid catalysed hydrolysis\",\"authors\":\"Aswini Kalita , Lakhminandan Goswami , Pankaj Gogoi , Subrata Paul\",\"doi\":\"10.1016/j.ica.2024.122408\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>One mono nuclear copper(II) complex (Cu-TPPS-OOCCH<sub>3</sub> with structural formula C<sub>17</sub>H<sub>19</sub>CuN<sub>6</sub>O<sub>3</sub>PS) is synthesized using a novel tripodal tetradentate ligand, tris-(2-pyridinylamino)phosphene sulphide (TPPS), which has three pyridinylamino groups attached to a phosphorus atom connected to a sulphur atom (P<img>S). The equatorial positions of the complex are occupied by three amino <em>N</em>-atoms of three aminopyridyl groups and one O-atom of the acetate group. The apical position is occupied by other O-atom of acetate group and one secondary <em>N</em>-atom of the tripodal ligand. The complex has been synthesized and purified as green solid and characterized by various spectroscopic techniques and the structure has been determined by X-ray single crystal diffraction study. The geometry optimizations and calculations of energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the compounds are performed by using the hybrid B3LYP density functional theory (DFT) along with the def2TZVP basis set.</div></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":\"574 \",\"pages\":\"Article 122408\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-10-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004997\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004997","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
本研究利用一种新型三足式四价配体--三(2-吡啶基氨基)硫化磷(TPPS)合成了一种单核铜(II)配合物(Cu-TPPS-OOCCH3,结构式为 C17H19CuN6O3PS)。复合物的赤道位置由三个氨基吡啶基的三个氨基 N 原子和一个醋酸基的 O 原子占据。顶端位置由醋酸基团的另一个 O 原子和三元配体的一个仲 N 原子占据。该复合物已合成并纯化为绿色固体,并通过各种光谱技术进行了表征,其结构已通过 X 射线单晶衍射研究确定。利用混合 B3LYP 密度泛函理论(DFT)和 def2TZVP 基集对化合物的几何形状进行了优化,并计算了最高占有分子轨道(HOMO)和最低未占有分子轨道(LUMO)的能量。
Synthesis, Characterization, Crystal structure determination and DFT study of a six coordinated Cu (II) complex of a phosphorous based tris-(2-pyridinylamino) phosphene sulphide ligand and its acid catalysed hydrolysis
One mono nuclear copper(II) complex (Cu-TPPS-OOCCH3 with structural formula C17H19CuN6O3PS) is synthesized using a novel tripodal tetradentate ligand, tris-(2-pyridinylamino)phosphene sulphide (TPPS), which has three pyridinylamino groups attached to a phosphorus atom connected to a sulphur atom (PS). The equatorial positions of the complex are occupied by three amino N-atoms of three aminopyridyl groups and one O-atom of the acetate group. The apical position is occupied by other O-atom of acetate group and one secondary N-atom of the tripodal ligand. The complex has been synthesized and purified as green solid and characterized by various spectroscopic techniques and the structure has been determined by X-ray single crystal diffraction study. The geometry optimizations and calculations of energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the compounds are performed by using the hybrid B3LYP density functional theory (DFT) along with the def2TZVP basis set.
期刊介绍:
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.