Debipada Chatterjee, Sampad Shyamal and Sundargopal Ghosh*,
{"title":"[Cp*Os] （Cp* = η - c5me5）配位球中稳定的二硼烷和双（硼基）锇配合物","authors":"Debipada Chatterjee, Sampad Shyamal and Sundargopal Ghosh*, ","doi":"10.1021/acs.organomet.5c0007610.1021/acs.organomet.5c00076","DOIUrl":null,"url":null,"abstract":"<p >Electron-precise osmium boron complexes have been synthesized and structurally characterized with similarity to [B<sub>2</sub>H<sub>6</sub>]. Thermolysis of an unstable intermediate, generated from the reaction of [(Cp*OsBr<sub>2</sub>)<sub>2</sub>], <b>1</b>, and [LiBH<sub>4</sub>·THF], with CO gas led to the formation of colorless [Cp*Os(CO)<sub>2</sub>(η<sup>2</sup>-B<sub>2</sub>H<sub>5</sub>)], <b>2</b>. Complex <b>2</b> is analogous to diborane(6) [B<sub>2</sub>H<sub>6</sub>], in which one of the bridging hydrogens is replaced by a [Cp*Os(CO)<sub>2</sub>] fragment. With an objective to isolate Os-diborane species supported by aryl chalcogenide fragments, we have treated <b>1</b> with an in situ generated chalcogenoborate species [LiBH<sub>3</sub>(SePh)]. The reaction yielded [(Cp*Os)<sub>2</sub>(μ-(HB)O(BH)-κ<sup>2</sup>B:κ<sup>2</sup>B)(μ-SePh)<sub>2</sub>], <b>3</b>, in which an oxadiborirane unit is coordinated to two [Cp*Os] fragments. In contrast, the thermolysis of an osmium intermediate, generated from the reaction of [(Cp*OsBr<sub>2</sub>)<sub>2</sub>], <b>1</b>, and [LiBH<sub>4</sub>·THF], with [S<sub>2</sub>Ph<sub>2</sub>] yielded a bis(boryl) complex, [(Cp*Os)<sub>2</sub>(μ-HBS(1,2-C<sub>6</sub>H<sub>4</sub>)BS-κ<sup>2</sup>B:κ<sup>2</sup>B:κ<sup>2</sup>S)(μ-SPh)], <b>4</b>. All the complexes have been characterized by multinuclear NMR and IR spectroscopies, mass spectrometry, and single-crystal X-ray diffraction studies. Additionally, density functional theory (DFT) calculations are carried out that afford insight into the bonding of complexes <b>2</b>–<b>4</b>.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 10","pages":"1075–1087 1075–1087"},"PeriodicalIF":2.5000,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Diborane and Bis(boryl) Complexes of Osmium Stabilized in the Coordination Sphere of [Cp*Os] (Cp* = η5-C5Me5)\",\"authors\":\"Debipada Chatterjee, Sampad Shyamal and Sundargopal Ghosh*, \",\"doi\":\"10.1021/acs.organomet.5c0007610.1021/acs.organomet.5c00076\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Electron-precise osmium boron complexes have been synthesized and structurally characterized with similarity to [B<sub>2</sub>H<sub>6</sub>]. Thermolysis of an unstable intermediate, generated from the reaction of [(Cp*OsBr<sub>2</sub>)<sub>2</sub>], <b>1</b>, and [LiBH<sub>4</sub>·THF], with CO gas led to the formation of colorless [Cp*Os(CO)<sub>2</sub>(η<sup>2</sup>-B<sub>2</sub>H<sub>5</sub>)], <b>2</b>. Complex <b>2</b> is analogous to diborane(6) [B<sub>2</sub>H<sub>6</sub>], in which one of the bridging hydrogens is replaced by a [Cp*Os(CO)<sub>2</sub>] fragment. With an objective to isolate Os-diborane species supported by aryl chalcogenide fragments, we have treated <b>1</b> with an in situ generated chalcogenoborate species [LiBH<sub>3</sub>(SePh)]. The reaction yielded [(Cp*Os)<sub>2</sub>(μ-(HB)O(BH)-κ<sup>2</sup>B:κ<sup>2</sup>B)(μ-SePh)<sub>2</sub>], <b>3</b>, in which an oxadiborirane unit is coordinated to two [Cp*Os] fragments. In contrast, the thermolysis of an osmium intermediate, generated from the reaction of [(Cp*OsBr<sub>2</sub>)<sub>2</sub>], <b>1</b>, and [LiBH<sub>4</sub>·THF], with [S<sub>2</sub>Ph<sub>2</sub>] yielded a bis(boryl) complex, [(Cp*Os)<sub>2</sub>(μ-HBS(1,2-C<sub>6</sub>H<sub>4</sub>)BS-κ<sup>2</sup>B:κ<sup>2</sup>B:κ<sup>2</sup>S)(μ-SPh)], <b>4</b>. All the complexes have been characterized by multinuclear NMR and IR spectroscopies, mass spectrometry, and single-crystal X-ray diffraction studies. 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Diborane and Bis(boryl) Complexes of Osmium Stabilized in the Coordination Sphere of [Cp*Os] (Cp* = η5-C5Me5)
Electron-precise osmium boron complexes have been synthesized and structurally characterized with similarity to [B2H6]. Thermolysis of an unstable intermediate, generated from the reaction of [(Cp*OsBr2)2], 1, and [LiBH4·THF], with CO gas led to the formation of colorless [Cp*Os(CO)2(η2-B2H5)], 2. Complex 2 is analogous to diborane(6) [B2H6], in which one of the bridging hydrogens is replaced by a [Cp*Os(CO)2] fragment. With an objective to isolate Os-diborane species supported by aryl chalcogenide fragments, we have treated 1 with an in situ generated chalcogenoborate species [LiBH3(SePh)]. The reaction yielded [(Cp*Os)2(μ-(HB)O(BH)-κ2B:κ2B)(μ-SePh)2], 3, in which an oxadiborirane unit is coordinated to two [Cp*Os] fragments. In contrast, the thermolysis of an osmium intermediate, generated from the reaction of [(Cp*OsBr2)2], 1, and [LiBH4·THF], with [S2Ph2] yielded a bis(boryl) complex, [(Cp*Os)2(μ-HBS(1,2-C6H4)BS-κ2B:κ2B:κ2S)(μ-SPh)], 4. All the complexes have been characterized by multinuclear NMR and IR spectroscopies, mass spectrometry, and single-crystal X-ray diffraction studies. Additionally, density functional theory (DFT) calculations are carried out that afford insight into the bonding of complexes 2–4.
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.
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