The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex

The photochemical reaction of Tp′Rh(L)(η2-PhN=L) [Tp′ = tris-(3,5-dimethyl pyrazolyl)borate, L = CNCH2CMe3] to form the coordinatively unsaturated reactive fragment, [Tp′Rh(L)], in the presence of alkylnitriles has been studied. The [Tp′Rh(L)] complex has been shown to selectively activate the primary CH terminus of acetonitrile, propionitrile, butyronitrile, and valeronitrile. The resulting hydrides showed uncharacteristic stability in the presence of C6D6 and their rates of reductive elimination were monitored by 1H NMR spectroscopy. Competition reactions permit the establishment of the relative stabilities of the activation products.