Abstract
Improved procedures are reported for the preparation of nitroso-carboranes RCb°NO (Cb° = 1,2-C 2B 10H 10; R = Ph, Me at cage carbon C2) in 44–77% yield, and of dicarboranylamines (RCb°) 2NH in 55–65% yield by reactions between the lithio-carboranes, RCb°Li and nitrosyl chloride, NOCl, in cold mixtures of diethyl ether and either pentane (for RCb°NO) or dimethoxyethane (for (RCb°) 2NH). Deprotonation of the amines by KO tBu in toluene in the presence of 18-crown-6, (CH 2CH 2O) 6, affords the salts [K(18-crown-6)] +[(RCb°) 2N] −. X-ray crystal structures of PhCb°NO, (PhCb°) 2NH, (MeCb°) 2NH and [K(18-crown-6)] +[(PhCb°) 2N] − are described, and the bonding implications of their cage C…C distances (1.68, 1.80, 1.75 and 1.99 Å, respectively) are discussed. These species provide further striking examples of the remarkable capacity of the ortho-carborane cage to act as a sensitive indicator of the π-donor characteristics of ligands attached to its cage carbon atoms.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
