{"title":"Metal-Rich Fused Clusters: Syntheses, Structures, and Bonding of Heteronuclear Condensed Metallaboranes","authors":"Shippy Jaiswal, Alaka Nanda Pradhan, Sundargopal Ghosh","doi":"10.1021/acs.organomet.4c00288","DOIUrl":null,"url":null,"abstract":"Syntheses and structural elucidations of a series of condensed clusters are described. The condensation of <i>nido</i>-[(Cp*Ru)<sub>2</sub>(B<sub>3</sub>H<sub>9</sub>)], <i>nido</i>-<b>1</b>, with heavier group 7 metal carbonyl, [Re<sub>2</sub>(CO)<sub>10</sub>], yielded [(Cp*Ru)<sub>2</sub>(CO)B<sub>3</sub>H<sub>8</sub>{Re(CO)<sub>3</sub>}], <b>2</b>. Ruthenaborane <b>2</b> is an edge-fused cluster of square pyramid {RuReB<sub>3</sub>} and triangle {RuB<sub>2</sub>} through a B–B bond. Further, the reaction of <i>arachno</i>-[(Cp*Ru)<sub>2</sub>(B<sub>3</sub>H<sub>8</sub>)(CS<sub>2</sub>H)], <i>arachno</i>-<b>3</b>, with [Co<sub>2</sub>(CO)<sub>8</sub>] led to the formation of condensed ruthenaboranes [(Cp*Ru)<sub>2</sub>B<sub>3</sub>H<sub>3</sub>S{Co<sub>3</sub>(CO)<sub>8</sub>}(SCH<sub>3</sub>)], <b>4</b>, and [(Cp*Ru)<sub>2</sub>B<sub>3</sub>H<sub>4</sub>{Co<sub>2</sub>(CO)<sub>7</sub>}(SCH<sub>3</sub>)], <b>5</b>. Cluster <b>4</b> comprises two tetrahedron {Co<sub>2</sub>RuB}, {Co<sub>2</sub>BS} and pentagonal pyramidal {Co<sub>2</sub>RuB<sub>3</sub>} cores, and cluster <b>5</b> consists of a butterfly {Ru<sub>2</sub>B<sub>2</sub>}, a triangle {CoB<sub>2</sub>}, and a tetrahedron {Co<sub>2</sub>B<sub>2</sub>}. Both clusters <b>4</b> and <b>5</b> do not follow Mingos’ fusion formalism for fused clusters and are unusual examples based on their composition. On the other hand, cluster <b>2</b> follows Mingos’ fusion formalism. All of the clusters have been characterized by <sup>1</sup>H, <sup>11</sup>B{<sup>1</sup>H}, <sup>13</sup>C{<sup>1</sup>H} NMR spectroscopies, electrospray ionization (ESI) mass spectrometry, and infrared (IR) spectroscopy, and the solid-state structures were established by single-crystal X-ray diffraction analysis.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00288","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
Abstract
Syntheses and structural elucidations of a series of condensed clusters are described. The condensation of nido-[(Cp*Ru)2(B3H9)], nido-1, with heavier group 7 metal carbonyl, [Re2(CO)10], yielded [(Cp*Ru)2(CO)B3H8{Re(CO)3}], 2. Ruthenaborane 2 is an edge-fused cluster of square pyramid {RuReB3} and triangle {RuB2} through a B–B bond. Further, the reaction of arachno-[(Cp*Ru)2(B3H8)(CS2H)], arachno-3, with [Co2(CO)8] led to the formation of condensed ruthenaboranes [(Cp*Ru)2B3H3S{Co3(CO)8}(SCH3)], 4, and [(Cp*Ru)2B3H4{Co2(CO)7}(SCH3)], 5. Cluster 4 comprises two tetrahedron {Co2RuB}, {Co2BS} and pentagonal pyramidal {Co2RuB3} cores, and cluster 5 consists of a butterfly {Ru2B2}, a triangle {CoB2}, and a tetrahedron {Co2B2}. Both clusters 4 and 5 do not follow Mingos’ fusion formalism for fused clusters and are unusual examples based on their composition. On the other hand, cluster 2 follows Mingos’ fusion formalism. All of the clusters have been characterized by 1H, 11B{1H}, 13C{1H} NMR spectroscopies, electrospray ionization (ESI) mass spectrometry, and infrared (IR) spectroscopy, and the solid-state structures were established by single-crystal X-ray diffraction analysis.
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.