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Presumably, the problems with methanol addition lie in the difficulty of completely freeing methanol from trace water.
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3-Benzyl complexes of nickel are known: Cámpora, J.; Gutiérrez, E.; Poveda, M. L.; Ruiz, C.; Carmona, E. J. Chem. Soc., Dalton Trans. 1992, 1769. Carmona, E.; Paneque, M.; Poveda, M. L. Polyhedron 1989, 8, 285.
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Unfortunately, we have not been able to isolate pure samples of ethyltetramethylcyclopentadienyl analogues of the nickel amido complexes in order to perform crossover experiments here.
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Ru-P), with N and O ligands giving the weakest Ru-P bond and C and H ligands giving the strongest Ru-P bond. In the system described here, the Ni-P bond lengths imply a similar trend (see ref 22). However, their phosphine dissociation was aided by π-bonding in the unsaturated intermediate; no such mechanism is possible for me complexes here (see ref 7). Since we have no way to accurately evaluate the Ni-P bond strengths, this effect is ignored here. Note that this does not invalidate our estimates of bond energy differences, because bond energies are defined to include changes in ancillary bonding (see footnote 34 in ref 87).
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85045499329
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Entropic factors in our system will be discussed more thoroughly below
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Since translational entropy is conserved. AS should be small in systems in which two particles are converted into two particles. See: Minas de Piedade, M. E.; Simões, J. A. M. J. Organomet. Chem. 1996, 518, 167. Entropic factors in our system will be discussed more thoroughly below.
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2) was shown to be largely due to a steric (entropic) effect. Large deviations were also observed for X ligands that bind through a second-row atom or can participate in backbonding.
-
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-
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78
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2642709150
-
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note
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nM and R (and, fortuitously, H-X BDE) held constant, the oxygen ligand binds more strongly than the nitrogen ligand.
-
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79
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2642712436
-
-
note
-
In this kind of graph, deviations from 1:1 behavior are dampened by the fact that both axes contain BDE(H-X). Thus, a systematic deviation from 1:1 behavior (such as that in ref 81) can appear to give a H-X/M-X graph with a slope nearly equal to 1.0.
-
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80
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2642708306
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note
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p(Ac). Thus, the deprotonation of benzoic acids is a poorer model for Ni-N/H-N exchange, as are other Hammett substituent constants.
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A reviewer has pointed out that these bond energies are undoubtedly affected by constructive π-interaction between M and X
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E = +0.10).
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5-Cp rings) leads us to believe that a simple associative mechanism is quite reasonable, the 18-electron "rule" (for which there are many exceptions) notwithstanding.
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See ref 96. We hope that others will carry out quantitative E-C analyses that test the generality of the notions presented here. Such studies should be performed on more robust systems than these nickel complexes, so that entropy changes can be evaluated, and so that decomposition does not limit the choice of ligands.
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Although the absolute temperature is not known to an accuracy of better than ±3 K, the temperature was maintained to ±0.1 K within each kinetic run using 4.
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