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As seen below, the excited sulfilimine can produce the nitrene and the isocyanate competitively
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GC-MS analysis indicated very small quantities of isomeric compounds, also of mass 281. These were interpreted as deriving from small isomeric impurities in the octene.
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GC-MS analysis indicated very small quantities of isomeric compounds, also of mass 281. These were interpreted as deriving from small isomeric impurities in the octene.
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It should also be noted that these are gas-phase calculations. Polar solvents would presumably favor the singlet state by a few kcal/mol
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It should also be noted that these are gas-phase calculations. Polar solvents would presumably favor the singlet state by a few kcal/mol.
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53
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45249087301
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In our experience, simplification of a molecule by reducing the first substituent methyl to a hydrogen atom, as in H2SO for (CH 3)2SO, for example, often leads to surprisingly different computational behavior of the simplified system, compared to the carbon-substituted analogues
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2SO, for example, often leads to surprisingly different computational behavior of the simplified system, compared to the carbon-substituted analogues.
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The singlet-triplet energy gap is undoubtedly also somewhat dependent on the solvent
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The singlet-triplet energy gap is undoubtedly also somewhat dependent on the solvent.
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55
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45249112194
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The Mulliken bond orders are better behaved with modest basis sets such as 6-31G(d,p). There are other, more sophisticated models of bond order, but these values serve as very adequate comparative and qualitative guides.
-
The Mulliken bond orders are better behaved with modest basis sets such as 6-31G(d,p). There are other, more sophisticated models of bond order, but these values serve as very adequate comparative and qualitative guides.
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