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Andrew D. Schwarz, Chee S. Onn and Prof. Philip Mountford A Remarkable Switch from a Diamination to a Hydrohydrazination Catalyst and Observation of an Unprecedented Catalyst Resting State Angewandte Chemie International Edition 51

Version of Record online: 4 NOV 2012 | DOI: 10.1002/anie.201206249

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A small change with a big effect: Reaction of the titanium complex 1 with terminal alkynes gave the unusual acetylide–vinylhydrazide(1−) compounds 2 (R=4-C6H4X (X=Me, CF3, OMe), C6F5, SiMe3) as hydrohydrazination intermediates. In contrast, a complex similar to 1 with bulkier trimethylsilyl substituents in place of the isopropyl groups is known to catalyze the 1,2-diamination of alkynes with hydrazines.

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