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- W2022145812 abstract "Enthalpies of reaction of Mn/sub 2/(CO)/sub 10/, Re/sub 2/(CO)/sub 10/, and MnRe(CO)/sub 10/ with iodine in cyclohexane solution are reported for 25 /sup 0/C, as obtained by the method of photocalorimetry. The photochemical reactions give the M(CO)/sub 5/I products cleanly with quantum yields of 0.41 +/- 0.01 (436 nm), 0.57 +/- 0.02 (366 nm), and 0.42 +/- 0.05 (366 nm) for the above systems, respectively, in good agreement with literature values. The ..delta..H/sub s,298/ values (s denoting solution) are -44.9 +/- 2.0 kcal for Mn/sub 3/(CO)/sub 10/(s) + I/sub 2/(s) = 2Mn(CO)/sub 5/I(s), -37.6 +/- 3.8 kcal for the analogous reaction of Re/sub 2/(CO)/sub 10/, and -55.7 +/- 3.0 kcal for MnRe(CO)/sub 10/(s) + I/sub 2/(s) = Mn(CO)/sub 5/I(s) + Re(CO)/sub 5/I(s). Also reported are the heats of solution of Mn/sub 2/(CO)/sub 10/(c) (c denoting crystalline state), Re/sub 2/(CO)/sub 10/(c), and Re(CO)/sub 5/I(c) in cyclohexane at 25 /sup 0/C, the respective values being 8.6 +/- 0.5, 8.2 +/- 0.5, and 8.3 +/- kcal mol/sup -1/. In the case of the manganese system, comparison of ..delta..H/sub c//sup 0/ (obtained by correcting ..delta..H/sub s,298/ for heats of solution) with that obtained from the literature values of ..delta..H/sub f//sup 0//sub 298/ of Mn/submore » 2/(CO)/sub 10/(c) and of Mn(CO)/sub 5/I(c) shows a discrepancy amounting to a correction of 9.6 kcal mol/sup -1/ if assigned entirely to the former ..delta..H/sub f//sup 0//sub 298/ value and of -4.6 kcal mol/sup -1/ if assigned entirely to the latter one. Combination of the ..delta..H/sub s,298/ values indicates that the Mn-Re bond in MnRe(CO)/sub 10/ is weaker by 15 kcal than the average of the corresponding metal-metal bond energies in Mn/sub 2/(CO)/sub 10/ and Re/sub 2/(CO)/sub 10/. The result contrasts considerably with that derived from bond energy values obtained from literature reports of ionization and appearance potentials.« less" @default.
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- W2022145812 date "1986-12-01" @default.
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- W2022145812 title "Photocalorimetry. 5. Enthalpies of reaction of M2(CO)10 (M = Mn, Re) compounds with iodine in cyclohexane solution at 25.degree.C" @default.
- W2022145812 doi "https://doi.org/10.1021/j100283a021" @default.
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