om501292k_si_002.cif (1.07 MB)

Coordination Induced Atropisomerism in an NHC-Based Rhodium Macrocycle

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posted on 09.03.2015, 00:00 by Rhiann E. Andrew, Dominic W. Ferdani, C. André Ohlin, Adrian B. Chaplin
Reversible interaction with carbon monoxide results in the onset of dynamic atropisomerism at 298 K in an otherwise static NHC-based rhodium pincer complex, [Rh­(C^N^C-(CH2)12)­(CO)]­[BArF4] (1, ArF = 3,5-C6H3(CF3)2). The mechanism of this process has been comprehensively interrogated by a combination of variable-temperature NMR spectroscopy, IR spectroscopy, and computational modeling. In addition, a structural analogue of a high-energy symmetrical intermediate speciesinvoked in the process but not directly observed spectroscopicallyhas been prepared and characterized in solution and the solid-state.