Dipanjan Mondal, Pawan Kumar, Joel T. Mague, Maravanji S. Balakrishna
{"title":"2,4,8,10-Tetra-tert-butyl-6-phenyldibenzo[d,g]-[1,3,6,2]dioxaselena-phosphocine Complexes：C-Se 键裂解及其氧化加成形成的新型八面体铑(III)配合物和 Hirshfeld 分析","authors":"Dipanjan Mondal, Pawan Kumar, Joel T. Mague, Maravanji S. Balakrishna","doi":"10.1007/s10870-023-00983-3","DOIUrl":null,"url":null,"abstract":"<div><p>Selenaphosphocine [(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)PhP] (<b>1</b>) on treatment with [Pd(COD)Cl<sub>2</sub>] yielded P,Se-coordinated complex [{(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)PhP}(PdCl<sub>2</sub>)] (<b>2</b>), whereas the reaction of <b>1</b> with [AuCl⋅SMe<sub>2</sub>] resulted in only P-coordinated complex [{(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)PhP}(AuCl)] (<b>4</b>). The reaction of <b>1</b> with [Rh(CO)<sub>2</sub>Cl]<sub>2</sub> in 4:1 molar ratio yielded a rare Rh<sup>III</sup> octahedral complex [{PhP(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)}{PPh(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>)(Se(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)}(RhCl)] (<b>3</b>) in good yield, in which one of the C–Se bonds of selenophosphocine is added oxidatively to Rh<sup>I</sup>. All of the complexes have been structurally characterized and are crystallized in the triclinic crystal system with <i>P</i>¯1 space group. All complexes showed intermolecular C–H⋯O and C–H ⋯Se hydrogen bonding interactions, that play major role in the crystal packing to form a three-dimensional array. In complex <b>2</b>, the crystal packing reveals the presence of rare intermolecular Pd⋯Cl interactions. Hirshfeld surface analysis, d<sub>norm</sub> and two-dimensional fingerprint plots were investigated to validate the contributions of the different intermolecular contacts within the supramolecular structure. A Hirshfeld surface analysis indicated that the most significant contributions to the crystal packing of <b>2</b> are from H⋯H (66.3%), C⋯H/H⋯C (13.5%), Cl⋯H/H⋯Cl (13.7%), Cl⋯C/C⋯Cl (1.8%) and Cl⋯C/C⋯Cl (1.0%) contacts, and those for <b>3</b> are from H⋯H (88.3%), C⋯H/H⋯C (8.3%) and Se⋯H/H⋯Se (3.6%) contacts, while those for <b>4</b> are from H⋯H (71.5%), C⋯H/H⋯C (9.9%), Cl⋯H/H⋯Cl (10.2%), Se⋯H/H⋯Se (2.7%) and Au⋯H/H⋯Au (1.7%) contacts.</p><h3>Graphical Abstract</h3><p>This paper describes the cleavage of a C–Se from dioxaselenaphosphocine and its oxidative addition to rhodium(I) complex and Hirshfeld analysis.</p>\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\n </div>","PeriodicalId":615,"journal":{"name":"Journal of Chemical Crystallography","volume":"53 3","pages":"438 - 452"},"PeriodicalIF":0.4000,"publicationDate":"2023-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"2,4,8,10-Tetra-tert-butyl-6-phenyldibenzo[d,g]-[1,3,6,2]dioxaselena-phosphocine Complexes: C–Se Bond Cleavage and Its Oxidative Addition to Form a Novel Octahedral Rhodium(III) Complex and Hirshfeld Analysis\",\"authors\":\"Dipanjan Mondal, Pawan Kumar, Joel T. Mague, Maravanji S. Balakrishna\",\"doi\":\"10.1007/s10870-023-00983-3\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Selenaphosphocine [(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)PhP] (<b>1</b>) on treatment with [Pd(COD)Cl<sub>2</sub>] yielded P,Se-coordinated complex [{(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)PhP}(PdCl<sub>2</sub>)] (<b>2</b>), whereas the reaction of <b>1</b> with [AuCl⋅SMe<sub>2</sub>] resulted in only P-coordinated complex [{(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)PhP}(AuCl)] (<b>4</b>). The reaction of <b>1</b> with [Rh(CO)<sub>2</sub>Cl]<sub>2</sub> in 4:1 molar ratio yielded a rare Rh<sup>III</sup> octahedral complex [{PhP(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>(<i>µ</i>-Se)(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)}{PPh(–OC<sub>6</sub>H<sub>2</sub>(<sup><i>t</i></sup>Bu)<sub>2</sub>)(Se(<sup><i>t</i></sup>Bu)<sub>2</sub>C<sub>6</sub>H<sub>2</sub>O–)}(RhCl)] (<b>3</b>) in good yield, in which one of the C–Se bonds of selenophosphocine is added oxidatively to Rh<sup>I</sup>. All of the complexes have been structurally characterized and are crystallized in the triclinic crystal system with <i>P</i>¯1 space group. All complexes showed intermolecular C–H⋯O and C–H ⋯Se hydrogen bonding interactions, that play major role in the crystal packing to form a three-dimensional array. In complex <b>2</b>, the crystal packing reveals the presence of rare intermolecular Pd⋯Cl interactions. Hirshfeld surface analysis, d<sub>norm</sub> and two-dimensional fingerprint plots were investigated to validate the contributions of the different intermolecular contacts within the supramolecular structure. A Hirshfeld surface analysis indicated that the most significant contributions to the crystal packing of <b>2</b> are from H⋯H (66.3%), C⋯H/H⋯C (13.5%), Cl⋯H/H⋯Cl (13.7%), Cl⋯C/C⋯Cl (1.8%) and Cl⋯C/C⋯Cl (1.0%) contacts, and those for <b>3</b> are from H⋯H (88.3%), C⋯H/H⋯C (8.3%) and Se⋯H/H⋯Se (3.6%) contacts, while those for <b>4</b> are from H⋯H (71.5%), C⋯H/H⋯C (9.9%), Cl⋯H/H⋯Cl (10.2%), Se⋯H/H⋯Se (2.7%) and Au⋯H/H⋯Au (1.7%) contacts.</p><h3>Graphical Abstract</h3><p>This paper describes the cleavage of a C–Se from dioxaselenaphosphocine and its oxidative addition to rhodium(I) complex and Hirshfeld analysis.</p>\\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\\n </div>\",\"PeriodicalId\":615,\"journal\":{\"name\":\"Journal of Chemical Crystallography\",\"volume\":\"53 3\",\"pages\":\"438 - 452\"},\"PeriodicalIF\":0.4000,\"publicationDate\":\"2023-04-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Crystallography\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10870-023-00983-3\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CRYSTALLOGRAPHY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Crystallography","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10870-023-00983-3","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CRYSTALLOGRAPHY","Score":null,"Total":0}
2,4,8,10-Tetra-tert-butyl-6-phenyldibenzo[d,g]-[1,3,6,2]dioxaselena-phosphocine Complexes: C–Se Bond Cleavage and Its Oxidative Addition to Form a Novel Octahedral Rhodium(III) Complex and Hirshfeld Analysis
Selenaphosphocine [(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)PhP] (1) on treatment with [Pd(COD)Cl2] yielded P,Se-coordinated complex [{(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)PhP}(PdCl2)] (2), whereas the reaction of 1 with [AuCl⋅SMe2] resulted in only P-coordinated complex [{(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)PhP}(AuCl)] (4). The reaction of 1 with [Rh(CO)2Cl]2 in 4:1 molar ratio yielded a rare RhIII octahedral complex [{PhP(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)}{PPh(–OC6H2(tBu)2)(Se(tBu)2C6H2O–)}(RhCl)] (3) in good yield, in which one of the C–Se bonds of selenophosphocine is added oxidatively to RhI. All of the complexes have been structurally characterized and are crystallized in the triclinic crystal system with P¯1 space group. All complexes showed intermolecular C–H⋯O and C–H ⋯Se hydrogen bonding interactions, that play major role in the crystal packing to form a three-dimensional array. In complex 2, the crystal packing reveals the presence of rare intermolecular Pd⋯Cl interactions. Hirshfeld surface analysis, dnorm and two-dimensional fingerprint plots were investigated to validate the contributions of the different intermolecular contacts within the supramolecular structure. A Hirshfeld surface analysis indicated that the most significant contributions to the crystal packing of 2 are from H⋯H (66.3%), C⋯H/H⋯C (13.5%), Cl⋯H/H⋯Cl (13.7%), Cl⋯C/C⋯Cl (1.8%) and Cl⋯C/C⋯Cl (1.0%) contacts, and those for 3 are from H⋯H (88.3%), C⋯H/H⋯C (8.3%) and Se⋯H/H⋯Se (3.6%) contacts, while those for 4 are from H⋯H (71.5%), C⋯H/H⋯C (9.9%), Cl⋯H/H⋯Cl (10.2%), Se⋯H/H⋯Se (2.7%) and Au⋯H/H⋯Au (1.7%) contacts.
Graphical Abstract
This paper describes the cleavage of a C–Se from dioxaselenaphosphocine and its oxidative addition to rhodium(I) complex and Hirshfeld analysis.
期刊介绍：
Journal of Chemical Crystallography is an international and interdisciplinary publication dedicated to the rapid dissemination of research results in the general areas of crystallography and spectroscopy. Timely research reports detail topics in crystal chemistry and physics and their relation to problems of molecular structure; structural studies of solids, liquids, gases, and solutions involving spectroscopic, spectrometric, X-ray, and electron and neutron diffraction; and theoretical studies.
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