High Lewis Acidity at Planar, Trivalent, and Neutral
Bismuth Centers
Posted on 2020-07-15 - 16:35
Geometric perturbation
away from classical structures can engender
unusual frontier MO situations leading to high Lewis acidity. Recently
we reported a T-shaped bismuth triamide, which exhibited planar Lewis
acidity that was unprecedented for neutral group 15 compounds. We
now report a comprehensive computational assessment of the origins
of planar Lewis acidity in such compounds. We subsequently use several
metrics such as MO energies, the Global Electrophilicity Index, ligand
coordination strengths, and fluoride ion affinity to show that electronic
variation can be combined with the unusual geometry at bismuth to
achieve fine-tuning of Lewis acid strength. Our calculations reveal
for the first time a surprisingly high electrophilicity, comparable
to or exceeding that of polyfluorinated triarylboranes, as well as
high rigidity at neutral planar bismuth triamides. These results foreshadow
the potentially broad applications of a hitherto unexplored class
of compounds, planar bismuthanes, in contexts that are currently dominated
by Lewis acidic triarylboranes.
CITE THIS COLLECTION
DataCiteDataCite
3 Biotech3 Biotech
3D Printing in Medicine3D Printing in Medicine
3D Research3D Research
3D-Printed Materials and Systems3D-Printed Materials and Systems
4OR4OR
AAPG BulletinAAPG Bulletin
AAPS OpenAAPS Open
AAPS PharmSciTechAAPS PharmSciTech
Abhandlungen aus dem Mathematischen Seminar der Universität HamburgAbhandlungen aus dem Mathematischen Seminar der Universität Hamburg
ABI Technik (German)ABI Technik (German)
Academic MedicineAcademic Medicine
Academic PediatricsAcademic Pediatrics
Academic PsychiatryAcademic Psychiatry
Academic QuestionsAcademic Questions
Academy of Management DiscoveriesAcademy of Management Discoveries
Academy of Management JournalAcademy of Management Journal
Academy of Management Learning and EducationAcademy of Management Learning and Education
Academy of Management PerspectivesAcademy of Management Perspectives
Academy of Management ProceedingsAcademy of Management Proceedings
Academy of Management ReviewAcademy of Management Review
Marczenko, Katherine
M.; Jee, Samantha; Chitnis, Saurabh S. (2020). High Lewis Acidity at Planar, Trivalent, and Neutral
Bismuth Centers. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.0c00378