Leobardo Rodriguez Segura, Kyle J. McGuire, Adharsh Raghavan, Jeremy J. Roos and Tong Ren*,
{"title":"含烯基或 1-氮杂-2-钴环丙烷分子的 CoIII(TIM) 配合物的合成与表征","authors":"Leobardo Rodriguez Segura, Kyle J. McGuire, Adharsh Raghavan, Jeremy J. Roos and Tong Ren*, ","doi":"10.1021/acs.organomet.4c00113","DOIUrl":null,"url":null,"abstract":"<p >Reported herein are the synthesis and characterization of mono- and bis-alkenyl Co<sup>III</sup>(TIM) (TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) complexes along with products containing a 1-aza-2-cobalt-cyclopropane unit. The <i>trans</i>-[Co(TIM)(C(CH<sub>2</sub>)Ar)Cl]<sup>+</sup>-type (Ar = phenyl (Ph, <b>1a</b>), −C<sub>6</sub>H<sub>4</sub>-4-<sup>t</sup>Bu (<b>1b</b>), and −C<sub>6</sub>F<sub>5</sub> (<b>1c</b>)), <i>trans</i>-[Co(TIM)(C(CH<sub>2</sub>)Ar)<sub>2</sub>]<sup>+</sup>-type (Ar = Ph (<b>2a</b>) and −C<sub>6</sub>F<sub>5</sub> (<b>2c</b>)), and <i>trans</i>-[Co(TIM″)(C(CH<sub>3</sub>)Ar)Cl]<sup>+</sup>-type complexes (Ar = Ph (<b>3a</b>) and −C<sub>6</sub>H<sub>4</sub>-4-<sup>t</sup>Bu (<b>3b</b>); TIM″ is the resultant derivative of TIM) were prepared from the reaction between <i>trans</i>-[Co(TIM)Cl<sub>2</sub>]PF<sub>6</sub> and the corresponding terminal aryl alkyne in the presence of NaBH<sub>4</sub>. Molecular structures of <b>1a</b>/<b>c</b>, <b>2a</b>/<b>c</b>, and <b>3a</b> were established via single-crystal X-ray diffraction studies. Characterization using <sup>1</sup>H NMR further confirmed the occurrence of either an alkenyl (<b>1</b> and <b>2</b>) or 1-aza-2-cobalt-cyclopropane (<b>3</b>). The absorption spectra of <b>1</b> and <b>3</b> reveal differences in the optical HOMO–LUMO gaps with well-defined d–d bands at 477 and 512 nm for <b>1a</b> and <b>3a</b>, respectively. Cyclic voltammograms of <b>1</b> and <b>2</b> consist of an irreversible oxidation and an irreversible reduction characteristic of the Co<sup>III</sup> center, while those of <b>3</b> display two reduction events. Density functional theory calculations were performed to investigate the bonding and electronic structures of <b>1a</b>–<b>3a</b>. Natural bonding orbital calculations on <b>3a</b> suggest significant stabilization in donor → acceptor resonance-type interactions afforded by the 1-aza-2-cobalt-cyclopropane unit.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and Characterization of CoIII(TIM) Complexes Bearing Alkenyl or 1-Aza-2-cobalt-cyclopropane Moieties\",\"authors\":\"Leobardo Rodriguez Segura, Kyle J. McGuire, Adharsh Raghavan, Jeremy J. Roos and Tong Ren*, \",\"doi\":\"10.1021/acs.organomet.4c00113\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Reported herein are the synthesis and characterization of mono- and bis-alkenyl Co<sup>III</sup>(TIM) (TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) complexes along with products containing a 1-aza-2-cobalt-cyclopropane unit. The <i>trans</i>-[Co(TIM)(C(CH<sub>2</sub>)Ar)Cl]<sup>+</sup>-type (Ar = phenyl (Ph, <b>1a</b>), −C<sub>6</sub>H<sub>4</sub>-4-<sup>t</sup>Bu (<b>1b</b>), and −C<sub>6</sub>F<sub>5</sub> (<b>1c</b>)), <i>trans</i>-[Co(TIM)(C(CH<sub>2</sub>)Ar)<sub>2</sub>]<sup>+</sup>-type (Ar = Ph (<b>2a</b>) and −C<sub>6</sub>F<sub>5</sub> (<b>2c</b>)), and <i>trans</i>-[Co(TIM″)(C(CH<sub>3</sub>)Ar)Cl]<sup>+</sup>-type complexes (Ar = Ph (<b>3a</b>) and −C<sub>6</sub>H<sub>4</sub>-4-<sup>t</sup>Bu (<b>3b</b>); TIM″ is the resultant derivative of TIM) were prepared from the reaction between <i>trans</i>-[Co(TIM)Cl<sub>2</sub>]PF<sub>6</sub> and the corresponding terminal aryl alkyne in the presence of NaBH<sub>4</sub>. Molecular structures of <b>1a</b>/<b>c</b>, <b>2a</b>/<b>c</b>, and <b>3a</b> were established via single-crystal X-ray diffraction studies. Characterization using <sup>1</sup>H NMR further confirmed the occurrence of either an alkenyl (<b>1</b> and <b>2</b>) or 1-aza-2-cobalt-cyclopropane (<b>3</b>). The absorption spectra of <b>1</b> and <b>3</b> reveal differences in the optical HOMO–LUMO gaps with well-defined d–d bands at 477 and 512 nm for <b>1a</b> and <b>3a</b>, respectively. Cyclic voltammograms of <b>1</b> and <b>2</b> consist of an irreversible oxidation and an irreversible reduction characteristic of the Co<sup>III</sup> center, while those of <b>3</b> display two reduction events. Density functional theory calculations were performed to investigate the bonding and electronic structures of <b>1a</b>–<b>3a</b>. Natural bonding orbital calculations on <b>3a</b> suggest significant stabilization in donor → acceptor resonance-type interactions afforded by the 1-aza-2-cobalt-cyclopropane unit.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-04-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00113\",\"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":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00113","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Synthesis and Characterization of CoIII(TIM) Complexes Bearing Alkenyl or 1-Aza-2-cobalt-cyclopropane Moieties
Reported herein are the synthesis and characterization of mono- and bis-alkenyl CoIII(TIM) (TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) complexes along with products containing a 1-aza-2-cobalt-cyclopropane unit. The trans-[Co(TIM)(C(CH2)Ar)Cl]+-type (Ar = phenyl (Ph, 1a), −C6H4-4-tBu (1b), and −C6F5 (1c)), trans-[Co(TIM)(C(CH2)Ar)2]+-type (Ar = Ph (2a) and −C6F5 (2c)), and trans-[Co(TIM″)(C(CH3)Ar)Cl]+-type complexes (Ar = Ph (3a) and −C6H4-4-tBu (3b); TIM″ is the resultant derivative of TIM) were prepared from the reaction between trans-[Co(TIM)Cl2]PF6 and the corresponding terminal aryl alkyne in the presence of NaBH4. Molecular structures of 1a/c, 2a/c, and 3a were established via single-crystal X-ray diffraction studies. Characterization using 1H NMR further confirmed the occurrence of either an alkenyl (1 and 2) or 1-aza-2-cobalt-cyclopropane (3). The absorption spectra of 1 and 3 reveal differences in the optical HOMO–LUMO gaps with well-defined d–d bands at 477 and 512 nm for 1a and 3a, respectively. Cyclic voltammograms of 1 and 2 consist of an irreversible oxidation and an irreversible reduction characteristic of the CoIII center, while those of 3 display two reduction events. Density functional theory calculations were performed to investigate the bonding and electronic structures of 1a–3a. Natural bonding orbital calculations on 3a suggest significant stabilization in donor → acceptor resonance-type interactions afforded by the 1-aza-2-cobalt-cyclopropane unit.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.