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note
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To determine whether this represents incomplete reaction or the thermodynamic ratio of 2/3 at this temperature, we heated 2a,b at 140°C in dimethylcyclopropane. Unfortunately, we were not able to detect the expected small amount of 3 by NMR spectrometry before irreversible decomposition began to set in. We therefore cannot rigorously establish that the 98/2 ratio of 2/3 represents the equilibrium ratio at this temperature.
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note
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6.
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85034304254
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note
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Three Fortran programs were used to fit the data using numerical integration and least-squares nonlinear regression: Gear (v. 2.1) and Git (v. 2.1) were written by R. J. McKinney and F. J. Weigert at E. I. DuPont & Nemours Co., and Calkinetics (v. 1.0) was written by J. Krom (currently at Cornell University). The results obtained using Gear and Git agreed with those using Calkinetics.
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52
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85034300042
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note
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In the alkane complex, the iridium center now acts as a prochiral center. To facilitate the discussion: (a) we assume the three atoms, P, Ir, and H (of the alkane ligand), are coplanar with the centroid of the cyclpentadienyl ring; (b) we have arbitrarily defined the direction of insertion of the iridium center into the C-H bond to always proceed toward the second, unbound C-H bond of the alkane ligand; (c) when defining the priority of the C center for stereochemical (R,S) assignments, the H bound to the iridium has the highest priority; this prevents changing of R and S designation solely due to changes in priority. Note that this is not the accepted system for priority.
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