David H.I. Maier, Frederick J.F. Jacobs, Barend C.B. Bezuidenhoudt, Alice Brink, Charlene Marais
{"title":"1,2-双(2-溴苯基)乙炔:5 ' -甲氧基和5 ' -二氟甲氧基对电子性质和关键键长的影响","authors":"David H.I. Maier, Frederick J.F. Jacobs, Barend C.B. Bezuidenhoudt, Alice Brink, Charlene Marais","doi":"10.1016/j.ica.2025.122773","DOIUrl":null,"url":null,"abstract":"<div><div>The effect of methoxy and difluoromethoxy groups para to the bromo substituent of 1,2-bis(2-bromophenyl)ethynes on the conformation of the molecule and the properties of the C<img>C and C<img>Br bonds was investigated by single crystal X-ray diffractometry and Nuclear Magnetic Resonance spectroscopy. The difluoromethoxy and methoxy groups both activated the <em>ortho</em> positions, as was evident from the shielding of both the proton and carbon atoms at these positions in NMR experiments. The C<sub>6</sub>-C≡C-C<sub>6</sub> system in 1,2-bis(2-bromophenyl)ethyne, 1,2-bis(2-bromo-5-(difluoromethoxy)phenyl)ethyne, 1,2-bis(2-bromo-5-methoxyphenyl)ethyne and 1-bromo-2-((2-bromophenyl)ethynyl)-4-methoxybenzene is in effect coplanar, with the dihedral angle between the two ring planes ranging from 0° to 5.8°. Substitution has little effect on the electronic properties of the triple bond, as was evident from the similar <sup>13</sup>C NMR spectroscopy chemical shifts and crystallographic bond distances. This is also reflected in the similar angles at the sp- centra, which deviate only slightly from linearity (177.3(2) – 179.6(1)°). The OCF<sub>2</sub>H substituent resulted in a small contraction of the C<img>Br bond and OCH<sub>3</sub> in a slight elongation. The bromo-bearing carbon was shielded with 3.8 ppm by the OCF<sub>2</sub>H group and by more than 9 ppm relative to an H atom by the OCH<sub>3</sub> group in <sup>13</sup>C NMR spectroscopy experiments.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"586 ","pages":"Article 122773"},"PeriodicalIF":2.7000,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"1,2-Bis(2-bromophenyl)ethynes: The influence of 5′-methoxy and 5′-difluoromethoxy groups on the electronic properties and crucial bond lengths\",\"authors\":\"David H.I. Maier, Frederick J.F. Jacobs, Barend C.B. Bezuidenhoudt, Alice Brink, Charlene Marais\",\"doi\":\"10.1016/j.ica.2025.122773\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The effect of methoxy and difluoromethoxy groups para to the bromo substituent of 1,2-bis(2-bromophenyl)ethynes on the conformation of the molecule and the properties of the C<img>C and C<img>Br bonds was investigated by single crystal X-ray diffractometry and Nuclear Magnetic Resonance spectroscopy. The difluoromethoxy and methoxy groups both activated the <em>ortho</em> positions, as was evident from the shielding of both the proton and carbon atoms at these positions in NMR experiments. The C<sub>6</sub>-C≡C-C<sub>6</sub> system in 1,2-bis(2-bromophenyl)ethyne, 1,2-bis(2-bromo-5-(difluoromethoxy)phenyl)ethyne, 1,2-bis(2-bromo-5-methoxyphenyl)ethyne and 1-bromo-2-((2-bromophenyl)ethynyl)-4-methoxybenzene is in effect coplanar, with the dihedral angle between the two ring planes ranging from 0° to 5.8°. Substitution has little effect on the electronic properties of the triple bond, as was evident from the similar <sup>13</sup>C NMR spectroscopy chemical shifts and crystallographic bond distances. This is also reflected in the similar angles at the sp- centra, which deviate only slightly from linearity (177.3(2) – 179.6(1)°). The OCF<sub>2</sub>H substituent resulted in a small contraction of the C<img>Br bond and OCH<sub>3</sub> in a slight elongation. The bromo-bearing carbon was shielded with 3.8 ppm by the OCF<sub>2</sub>H group and by more than 9 ppm relative to an H atom by the OCH<sub>3</sub> group in <sup>13</sup>C NMR spectroscopy experiments.</div></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":\"586 \",\"pages\":\"Article 122773\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2025-05-20\",\"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/S0020169325002397\",\"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/S0020169325002397","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
1,2-Bis(2-bromophenyl)ethynes: The influence of 5′-methoxy and 5′-difluoromethoxy groups on the electronic properties and crucial bond lengths
The effect of methoxy and difluoromethoxy groups para to the bromo substituent of 1,2-bis(2-bromophenyl)ethynes on the conformation of the molecule and the properties of the CC and CBr bonds was investigated by single crystal X-ray diffractometry and Nuclear Magnetic Resonance spectroscopy. The difluoromethoxy and methoxy groups both activated the ortho positions, as was evident from the shielding of both the proton and carbon atoms at these positions in NMR experiments. The C6-C≡C-C6 system in 1,2-bis(2-bromophenyl)ethyne, 1,2-bis(2-bromo-5-(difluoromethoxy)phenyl)ethyne, 1,2-bis(2-bromo-5-methoxyphenyl)ethyne and 1-bromo-2-((2-bromophenyl)ethynyl)-4-methoxybenzene is in effect coplanar, with the dihedral angle between the two ring planes ranging from 0° to 5.8°. Substitution has little effect on the electronic properties of the triple bond, as was evident from the similar 13C NMR spectroscopy chemical shifts and crystallographic bond distances. This is also reflected in the similar angles at the sp- centra, which deviate only slightly from linearity (177.3(2) – 179.6(1)°). The OCF2H substituent resulted in a small contraction of the CBr bond and OCH3 in a slight elongation. The bromo-bearing carbon was shielded with 3.8 ppm by the OCF2H group and by more than 9 ppm relative to an H atom by the OCH3 group in 13C NMR spectroscopy experiments.
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.