N,N-addition of frustrated Lewis pairs to nitric oxide: an easy entry to a unique family of aminoxyl radicals

The intramolecular cyclohexylene-bridged P/B frustrated Lewis pair [Mes(2)P-C(6)H(10)-B(C(6)F(5))(2)] 1b reacts rapidly with NO to give the persistent FLP-NO aminoxyl radical 2b formed by P/B addition to the nitrogen atom of NO. This species was fully characterized by X-ray diffraction, EPR and UV/vis spectroscopies, C,H,N elemental analysis, and DFT calculations. The reactive oxygen-centered radical 2b undergoes a H-atom abstraction (HAA) reaction with 1,4-cyclohexadiene to give the diamagnetic FLP-NOH product 3b. FLP-NO 2b reacts with toluene at 70 °C in an HAA/radical capture sequence to give a 1:1 mixture of FLP-NOH 3b and FLP-NO-CH(2)Ph 4b, both characterized by X-ray diffraction. Structurally related FLPs [Mes(2)P-CHR(1)-CHR(2)-B(C(6)F(5))(2)] 1c, 1d, and 1e react analogously with NO to give the respective persistent FLP-NO radicals 2c, 2d, and 2e, respectively, which show similar HAA and O-functionalization reactions. The FLP-NO-CHMePh 6b derived from 1-bromoethylbenzene undergoes NO-C bond cleavage at 120 °C with an activation energy of E(a) = 35(2) kcal/mol. Species 6b induces the controlled nitroxide-mediated radical polymerization (NMP) of styrene at 130 °C to give polystyrene with a polydispersity index of 1.3. The FLP-NO systems represent a new family of aminoxyl radicals that are easily available by N,N-cycloaddition of C(2)-bridged intramolecular P/B frustrated Lewis pairs to nitric oxide.     

NONCOOPERATIVE MANAGEMENT OF THE NORTHEAST ATLANTIC COD FISHERY: A FIRST MOVER ADVANTAGE

The point of departure for this analysis is Bjørndal and Lindroos [2012], who developed an empirical bioeconomic model to analyze cooperative and noncooperative management of Northeast Atlantic cod. In their analysis, only constant strategies were analyzed for noncooperative games. In this paper, nonconstant strategies are considered. Moreover, the fishery in question is characterized by cooperative management. What may happen in the real world is that one nation breaks the cooperative agreement by fishing in excess of its quota. Often, it takes time for the other agent to detect this and respond. In this paper, we allow this kind of delayed response into a two‐agent noncooperative game so that, if country 2 exceeds its quota, there will be a time lag before this is detected by country 1; moreover, there may also be a delay until country 1 is able to respond. Results show that the outcome critically depends on the length of these two lags as well as initial conditions.