Spin‐Orbit Effects in a Thallium Borohydride Stabilized by Coordination to Bis(diisopropylamino)Cyclopropenylidene (BAC)
Reaction of Tl(OTf) with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in THF results in formation of [Tl(BAC)<sub>2</sub>(OTf)] (1) in moderate yields. Subsequent reaction of 1 with [K][H<sub>2</sub>-9-BBN] ([H<sub>2</sub>-9-BBN]<sup>-</sup> = dihydrido 9-boratabicyclo[3.3.1]nonane) in THF results in formation of [Tl(BAC)(μ-H<sub>2</sub>-9-BBN)]<sub>2</sub> (3), also in moderate yield. Complex 3 is the first reported thallium borohydride. We attribute its thermal stability to the strong donor ability of the BAC co-ligand. Both 1 and 3 exhibit trigonal pyramidal geometries about Tl<sup>+</sup> in the solid-state, indicative of the presence of stereochemically active lone pairs. The hydride environment in 3 is calculated to exhibit a 3.9 ppm downfield shift attributed to spin-orbit effects from the adjacent Tl center.
Authors
- Jochen Autschbach (ORCID: https://orcid.org/0000-0001-9392-877X)
- Xiaojuan Yu (ORCID: https://orcid.org/0000-0001-9412-6170)
- Trevor W. Hayton (ORCID: https://orcid.org/0000-0003-4370-1424)
- Guang Wu (ORCID: https://orcid.org/0000-0001-7257-6648)
- Thien Hoang Nguyen (ORCID: https://orcid.org/0000-0003-1218-0910)
Institutions
- University of California, Santa Barbara (US)
- University at Buffalo, State University of New York (US)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-07-24
- DOI
- https://doi.org/10.1002/anie.202509732
- Citations
- 1
- Primary Topic
- Organoboron and organosilicon chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.94
Funders
- National Science Foundation