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2-methane complex is consistently shown throughout this paper with a symmetrically (via two hydrogen atoms) bonded methane. This is an arbitrarily chosen convention. It may also be unsymmetrically bonded, such that basically one C-H bond functions as a donor. Since rotation of bonded methane is extremely facile and practically activationless (see ref 42), our conclusions concerning H/D exchange (see discussion) do not depend on the exact geometry of η2-bonded methane.
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85034551629
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23
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85034548546
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note
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For the limitations of the temperature range, see the Supporting Information.
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24
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85034558278
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note
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The more restricted pressure range for the trans isomer stems from the fact that the glass walls accept protons under high pressure, which leads to isomerization to give the more reactive cis isomer. An enhancement in reactivity was observed under pressures higher than those plotted in Figure 3.
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25
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0001455787
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85034551421
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D, since it prevents formation of the Pt-H complex. However, the secondary isotope effect of six deuterium atoms will lead to a systematic error that could be as large as the uncertainty of our determination.
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85034545345
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It is important to note that isomerization to give the trans hydride 2b was not observed under these conditions. Although the equilibrium is not too unfavorable for interconversion of 2a into 2b, there is no low-energy path for an intramolecular isomerization. Obviously, the kinetic barrier for placing the methane hydrogen in SS2 trans to amine is higher than for the migration of the hydrogen into the cis position. This may be due to the kinetic trans effect of the amine donor, quite similar to the effect discussed below.
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34
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0030057443
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D of 5 at room temperature is the maximum kinetic isotope effect calculated from the Pt-H vibration frequency, whereas a value close to 3 was reported experimentally: Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961.
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39
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85034543293
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note
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A treatment of the complete system is possible, but unfortunately not simple. We treated the complete system shown in Scheme 3 using the computer algebra system MAPLE (Maple V.3, student version, 1981-1994, Waterloo Maple Software and University of Waterloo) The evaluation of [SS1], [SS2], and [SS1′] in terms of the rate constants is possible. The calculation of the rates for formation of intermediate (2a-C-D) and product leads to a system of two linear differential equations that can be solved. However, the solution is so complex (a multiterm expression that fills several pages) that no meaningful conclusion could be drawn.
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41
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0001094610
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