Abstract
A synthetic sequence involving the initial nucleophilic attack of the isoelectronic nido-5,6-C2B8H11- or nido-B10H13- anions at a nitrile carbon, followed by nitrile hydroboration and cage-insertion, has been found to yield new azacarborane clusters in good yields. Thus, the reaction of nido-5,6-C2B8H11- with refluxing acetonitrile gave the azatricarbaborane anion arachno-7-CH3-5,7,14,12-C3NB8H11- (1-) in 65% yield, while nido-B10H13- reacted with acetonitrile, benzyl cyanide, or CH313CN to give the azamonocarbaborane anions arachno-7-CH3-7,12-CNB10H13- (2a-), arachno-7-Bn-7,12-CNB10H13- (2b-), and arachno-7-CH3-7,12-13CNB10H13- (2a--13C), respectively. Single-crystal X-ray studies of the isoelectronic clusters, 1- and 2a-, showed that hydroboration of the nitrile occurred, with the resulting imino group inserting into the cage framework in a position bridging the B2 and B11 borons. Consistent with their arachno skeletal electron counts, 1- and 2a- have cage frameworks containing two six-membered open fac...
Published Version
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