Encapsulating Inorganic Acetylene, HBNH, Using Flanking Coordinative Interactions

• Published in: Angewandte Chemie International Edition Vol. 54; no. 36; pp. 10666 - 10669
• Main Authors: Swarnakar, Anindya K., Hering-Junghans, Christian, Nagata, Koichi, Ferguson, Michael J., McDonald, Robert, Tokitoh, Norihiro, Rivard, Eric
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.09.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Acetylene; Adducts; boron; carbenes; Computer applications; Construction materials; Coordination compounds; donor-acceptor systems; Encapsulating; Encapsulation; Fluorination; Isotopic labeling; Migration; Modular; multiple bonds; nitrogen; Parents; Radioactive labeling; Transformations; carbenes; donor-acceptor systems; multiple bonds; boron; nitrogen
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201504867

A stable donor–acceptor coordination complex of the elusive parent inorganic iminoborane HBNH (a structural analogue of acetylene) is reported. This species was generated via thermally induced N2 elimination/1,2‐H migration from a hydrido(azido)borane adduct NHC⋅BH2N3 (NHC=N‐heterocyclic carbene) in the presence of a fluorinated triarylborane. The mechanism of this process was also investigated by computational and isotopic labeling studies. This transformation represents a new and potentially modular route to unsaturated inorganic building blocks for advanced material synthesis. Lightning in a bottle: An adduct of the elusive parent “inorganic acetylene” HBNH was prepared from a main‐group azide by means of a general process consisting of N2 loss and 1,2‐hydrogen migration. The mechanism of this reaction was examined by calculations and isotope‐labeling studies.