Bairagi, S and Giri, S and Joshi, G and Jemmis, ED and Ghosh, S (2024) Stabilization of Ethane-Like Dianionic Diborane(6) in Monometallic Titanium Complexes and its Subsequent B(sp3)�B(sp3) Bond Cleavage. In: Angewandte Chemie - International Edition .
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Abstract
Treatment of Cp*TiCl3 with LiBH4 â� THF followed by thermolysis with Ph2E2 (E=S or Se) resulted in the formation of classical diborane(6) complexes, (Cp*Ti)(η4-B2H4LLâ�²) (L=C6H4E; Lâ�²=C6H5E; 1 a: E=S, 1 b: E=Se), stabilized at titanium template. To the best of our knowledge, they are the first examples of mono-metallic classical diborane(6) complexes. The bonding analysis and theoretical studies suggest that the stabilization of these diborane(6) species is due to the presence of four bridging ligands in ĸ4-fashion, where two of them are phenyl thiolates/selenolates that provide more electrons to the electron-deficient titanium center. Reactions of these diborane(6) species with M(CO)5 â� THF (M=Mo, W) led to the cleavage of the electron-precise B(sp3)â��B(sp3) bond that yielded ĸ3-hydridoborato complexes (Cp*Ti)(ĸ3-BH3R)(μ-EPh)2{M(CO)4} (2 aâ��c: R=H, 3 aâ��c: R=Ph). In an attempt to isolate the Te-analogue of 1 aâ��b, a similar reaction was performed; however, the complex was too unstable to be isolated. Interestingly, the treatment of this unstable intermediate with W(CO)5 â� THF yielded (Cp*Ti)(ĸ3-BH3R)(μ-TePh)2{W(CO)4} (2 d: R=H, 3 d: R=Ph) that are analogues of 2 aâ��c and 3 aâ��c, respectively. Formation of these species provide indirect evidence for the existence of unstable (Cp*Ti)(η4-B2H4LLâ�²) (L=C6H4Te; Lâ�²=C6H5Te; 1 c). © 2024 Wiley-VCH GmbH.
| Item Type: | Journal Article |
|---|---|
| Publication: | Angewandte Chemie - International Edition |
| Publisher: | John Wiley and Sons Inc |
| Additional Information: | The copyright for this article belongs to the authors. |
| Keywords: | Alkylation; Borate minerals; Complexation; Ethane; Ligands; Metal analysis; Selenium compounds; Tellurium compounds; Titanium dioxide, Bond cleavages; Bonding analysis; Chalcogens; Classical; Diborane; Metallics; Monometallics; Thermolyses; Titania; Titanium complexes, Thermoanalysis |
| Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry |
| Date Deposited: | 06 Dec 2024 17:07 |
| Last Modified: | 06 Dec 2024 17:07 |
| URI: | http://eprints.iisc.ac.in/id/eprint/87107 |
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