Thomas X. Gentner, Gerd M. Ballmann, Sumanta Banerjee, Alan R. Kennedy, Stuart D. Robertson* and Robert E. Mulvey*,
{"title":"双(氨基)烷基镁酸盐在合成分子铷和铯铱镁酸盐中的应用","authors":"Thomas X. Gentner, Gerd M. Ballmann, Sumanta Banerjee, Alan R. Kennedy, Stuart D. Robertson* and Robert E. Mulvey*, ","doi":"10.1021/acs.organomet.4c00190","DOIUrl":null,"url":null,"abstract":"<p >Rubidium and cesium are the least studied naturally occurring s-block metals in organometallic chemistry but are in plentiful supply from a sustainability viewpoint as highlighted in the periodic table of natural elements published by the European Chemical Society. This underdevelopment reflects the phenomenal success of organometallic compounds of lithium, sodium, and potassium, but interest in heavier congeners has started to grow. Here, the synthesis and structures of rubidium and cesium bis(amido)alkyl magnesiates [(AM)MgN′<sub>2</sub>alkyl]<sub>∞</sub>, where N′ is the simple heteroamide <sup>–</sup>N(SiMe<sub>3</sub>)(Dipp), and alkyl is <i>n</i>Bu or CH<sub>2</sub>SiMe<sub>3</sub>, are reported. More stable than their <i>n</i>Bu analogues, the reactivities of the CH<sub>2</sub>SiMe<sub>3</sub> magnesiates toward 1,4-cyclohexadiene are revealed. Though both reactions produce target hydrido-magnesiates [(AM)MgN′<sub>2</sub>H]<sub>2</sub> in crystalline form amenable to X-ray diffraction study, the cesium compound could only be formed in a trace quantity. These studies showed that the bulk of the <sup>–</sup>N(SiMe<sub>3</sub>)(Dipp) ligand was sufficient to restrict both compounds to dimeric structures. Bearing some resemblance to inverse crown complexes, each structure has [(AM)(N)(Mg)(N)]<sub>2</sub> ring cores but differ in having no AM-N bonds, instead Rb and Cs complete the rings by engaging in multihapto interactions with Dipp π-clouds. Moreover, their hydride ions occupy μ<sub>3</sub>-(AM)<sub>2</sub>Mg environments, compared to μ<sub>2</sub>-Mg<sub>2</sub> environments in inverse crowns.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00190","citationCount":"0","resultStr":"{\"title\":\"Application of Bis(amido)alkyl Magnesiates toward the Synthesis of Molecular Rubidium and Cesium Hydrido-magnesiates\",\"authors\":\"Thomas X. Gentner, Gerd M. Ballmann, Sumanta Banerjee, Alan R. Kennedy, Stuart D. Robertson* and Robert E. Mulvey*, \",\"doi\":\"10.1021/acs.organomet.4c00190\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Rubidium and cesium are the least studied naturally occurring s-block metals in organometallic chemistry but are in plentiful supply from a sustainability viewpoint as highlighted in the periodic table of natural elements published by the European Chemical Society. This underdevelopment reflects the phenomenal success of organometallic compounds of lithium, sodium, and potassium, but interest in heavier congeners has started to grow. Here, the synthesis and structures of rubidium and cesium bis(amido)alkyl magnesiates [(AM)MgN′<sub>2</sub>alkyl]<sub>∞</sub>, where N′ is the simple heteroamide <sup>–</sup>N(SiMe<sub>3</sub>)(Dipp), and alkyl is <i>n</i>Bu or CH<sub>2</sub>SiMe<sub>3</sub>, are reported. More stable than their <i>n</i>Bu analogues, the reactivities of the CH<sub>2</sub>SiMe<sub>3</sub> magnesiates toward 1,4-cyclohexadiene are revealed. Though both reactions produce target hydrido-magnesiates [(AM)MgN′<sub>2</sub>H]<sub>2</sub> in crystalline form amenable to X-ray diffraction study, the cesium compound could only be formed in a trace quantity. These studies showed that the bulk of the <sup>–</sup>N(SiMe<sub>3</sub>)(Dipp) ligand was sufficient to restrict both compounds to dimeric structures. Bearing some resemblance to inverse crown complexes, each structure has [(AM)(N)(Mg)(N)]<sub>2</sub> ring cores but differ in having no AM-N bonds, instead Rb and Cs complete the rings by engaging in multihapto interactions with Dipp π-clouds. 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Application of Bis(amido)alkyl Magnesiates toward the Synthesis of Molecular Rubidium and Cesium Hydrido-magnesiates
Rubidium and cesium are the least studied naturally occurring s-block metals in organometallic chemistry but are in plentiful supply from a sustainability viewpoint as highlighted in the periodic table of natural elements published by the European Chemical Society. This underdevelopment reflects the phenomenal success of organometallic compounds of lithium, sodium, and potassium, but interest in heavier congeners has started to grow. Here, the synthesis and structures of rubidium and cesium bis(amido)alkyl magnesiates [(AM)MgN′2alkyl]∞, where N′ is the simple heteroamide –N(SiMe3)(Dipp), and alkyl is nBu or CH2SiMe3, are reported. More stable than their nBu analogues, the reactivities of the CH2SiMe3 magnesiates toward 1,4-cyclohexadiene are revealed. Though both reactions produce target hydrido-magnesiates [(AM)MgN′2H]2 in crystalline form amenable to X-ray diffraction study, the cesium compound could only be formed in a trace quantity. These studies showed that the bulk of the –N(SiMe3)(Dipp) ligand was sufficient to restrict both compounds to dimeric structures. Bearing some resemblance to inverse crown complexes, each structure has [(AM)(N)(Mg)(N)]2 ring cores but differ in having no AM-N bonds, instead Rb and Cs complete the rings by engaging in multihapto interactions with Dipp π-clouds. Moreover, their hydride ions occupy μ3-(AM)2Mg environments, compared to μ2-Mg2 environments in inverse crowns.
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.